Heteroleptic carbene complexes and the use thereof in organic electronics

ABSTRACT

The present invention relates to heteroleptic complexes comprising a phenylimidazole or phenyltriazole unit bonded via a carbene bond to a central metal atom, and phenylimidazole ligands attached via a nitrogen-metal bond to the central atom, to OLEDs which comprise such heteroleptic complexes, to light-emitting layers comprising at least one such heteroleptic complex, to a device selected from the group consisting of illuminating elements, stationary visual display units and mobile visual display units comprising such an OLED, to the use of such a heteroleptic complex in OLEDs, for example as emitter, matrix material, charge transport material and/or charge blocker.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/294,403, filed Mar. 6, 2019, now allowed, which is a continuation ofU.S. patent application Ser. No. 13/504,725, filed Apr. 27, 2012, whichis a 35 U.S.C. § 371 National Stage Patent Application of InternationalPatent Application No. PCT/EP2010/066400, filed Oct. 28, 2010, whichclaims priority to U.S. Provisional Application No. 61/255,499, filedOct. 28, 2009, the entire disclosures of which are incorporated hereinby reference.

BACKGROUND OF THE INVENTION

The present invention relates to heteroleptic complexes comprising aphenylimidazole or phenyltriazole unit bonded via a carbene bond to acentral metal atom, and phenylimidazole ligands attached via anitrogen-metal bond to the central atom, to OLEDs which comprise suchheteroleptic complexes, to light-emitting layers comprising at least onesuch heteroleptic complex, to a device selected from the groupconsisting of illuminating elements, stationary visual display units andmobile visual display units comprising such an OLED, to the use of sucha heteroleptic complex in OLEDs, for example as emitter, matrixmaterial, charge transport material and/or charge blocker.

Organic Light-Emitting Diodes (OLEDs) exploit the property of materialsto emit light when they are excited by electrical current. OLEDs are ofparticular interest as an alternative to cathode ray tubes andliquid-crystal displays for production of flat visual display units.Owing to the very compact design and the intrinsically low powerconsumption, devices comprising OLEDs are suitable especially for mobileapplications, for example for applications in cellphones, laptops, etc.

In addition, white OLEDs give great advantages over the illuminationtechnologies known to date, especially a particularly high efficiency.

The prior art proposes numerous materials, examples of which includeheteroleptic complexes with iridium as the central metal atom, whichemit light on excitation by electrical current.

WO 2006/121811 A1 discloses phosphorescent heteroleptic metal complexeswhich comprise carbene ligands. The complexes specified in WO2006/121811 A1, for example iridium complexes, all havebenzimidazolocarbenes (benzimidazolylidenes) as carbene ligands.Compounds which have imidazolocarbenes (imidazolylidenes) ortriazolocarbenes (triazolylidenes) as ligands are not disclosed in WO2006/121811 A1.

WO 2006/067074 A1 likewise discloses electroluminescent heterolepticmetal complexes with carbene ligands. The noncarbene ligands usedinclude arylpyridines, arylpyrazoles and aryltriazoles. Use of2-phenyl-1H-imidazoles as noncarbene ligands is not disclosed in WO2006/067074 A1.

WO 2007/115981 discloses heteroleptic metal complexes comprising bothcarbene ligands and heterocyclic noncarbene ligands, a process forpreparation thereof, and the use of these compounds in OLEDs. Thecompounds disclosed by way of example in WO 2007/115981 do not comprisea combination of 2-phenyl-1H-imidazole ligands with an imidazolocarbene(imidazolylidene) ligand or a triazolocarbene (triazolylidene) ligand.

JP 2009057505 discloses optoelectronic components which comprisecompounds with tunable emission wavelength, high light emissionefficiency and long lifetime. The components according to this documentcomprise metal complexes which, as well as two ligands optionally joinedto one another, comprise at least one ligand attached to the metal atomfirstly via a carbene bond and secondly via a noncarbene bond. Nocombination of a 2-phenyl-1H-imidazole ligand with an imidazolocarbene(imidazolylidene) ligand or a triazolocarbene (triazolylidene) ligand isdisclosed.

Even though compounds which exhibit electroluminescence in the visibleregion, more particularly in the red, green and especially blue regionof the electromagnetic spectrum, for example iridium complexes, arealready known, the provision of alternative compounds which possess highquantum yields and exhibit long diode lifetimes is desirable. In thecontext of the present invention, electroluminescence is understood tomean both electrofluorescence and electrophosphorescence.

It is therefore an object of the present invention to providealternative iridium and platinum complexes which are suitable forelectroluminescence in the visible region, more particularly in the red,green and especially blue region of the electromagnetic spectrum, whichenables the production of full-color displays and white OLEDs. It is afurther object of the present invention to provide correspondingcomplexes which can be used as a mixture with a host compound (matrixmaterial) or in substance, i.e. in the absence of host substances, as alight-emitting layer in OLEDs. It is a further object of the presentinvention to provide corresponding complexes which have a high quantumyield and a high stability in diodes. The complexes should be usable asemitter, matrix material, charge transport material, especially holetransport material, or charge blocker in OLEDs.

BRIEF SUMMARY OF THE INVENTION

These objects are achieved in accordance with the invention byheteroleptic complexes of the general formula (I)

in which M, A¹, A², n, m, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², R¹³ and R¹⁴ are each defined as follows:

M is a metal atom selected from the group consisting of Ir and Pt,

A¹, A² are each independently N or C,

n, m are each independently 1 or 2, where, if M is Pt, the sum of n andm is 2, or, if M is Ir, the sum of n and m is 3,

R¹ is a linear or branched alkyl radical optionally interrupted by atleast one heteroatom, optionally bearing at least one functional groupand having 1 to 20 carbon atoms, cycloalkyl radical optionallyinterrupted by at least one heteroatom, optionally bearing at least onefunctional group and having 3 to 20 carbon atoms, substituted orunsubstituted aryl radical optionally interrupted by at least oneheteroatom, optionally bearing at least one functional group and having6 to 30 carbon atoms. substituted or unsubstituted heteroaryl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 5 to 18 carbon atoms and/orheteroatoms,

R², R³ are each independently hydrogen, linear or branched alkyl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 1 to 20 carbon atoms, cycloalkylradical optionally interrupted by at least one heteroatom, optionallybearing at least one functional group and having 3 to 20 carbon atoms,substituted or unsubstituted aryl radical optionally interrupted by atleast one heteroatom, optionally bearing at least one functional groupand having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylradical optionally interrupted by at least one heteroatom, optionallybearing at least one functional group and having 5 to 18 carbon atomsand/or heteroatoms,

R⁴, R⁵, R⁶, R⁷ are each independently hydrogen, substituent with donoror acceptor action, linear or branched alkyl radical optionallyinterrupted by at least one heteroatom, optionally bearing at least onefunctional group and having 1 to 20 carbon atoms, cycloalkyl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 3 to 20 carbon atoms, substitutedor unsubstituted aryl radical optionally interrupted by at least oneheteroatom, optionally bearing at least one functional group and having6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 5 to 18 carbon atoms and/orheteroatoms,

or

R⁴ and R⁵ or R⁵ and R^(B) and/or R⁶ and R⁷ together form a saturated,unsaturated or aromatic carbon ring optionally interrupted by at leastone heteroatom and having a total of 5 to 30 carbon atoms orheteroatoms,

R⁸, R⁹ are each independently a free electron pair if A¹ or A² is N, or,if A¹ or A² is C, hydrogen. linear or branched alkyl radical optionallyinterrupted by at least one heteroatom, optionally bearing at least onefunctional group and having 1 to 20 carbon atoms, cycloalkyl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 3 to 20 carbon atoms, substitutedor unsubstituted aryl radical optionally interrupted by at least oneheteroatom, optionally bearing at least one functional group and having6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 5 to 18 carbon atoms and/orheteroatoms,

R¹⁰ is a linear or branched alkyl radical optionally interrupted by atleast one heteroatom, optionally bearing at least one functional groupand having 1 to 20 carbon atoms, cycloalkyl radical optionallyinterrupted by at least one heteroatom, optionally bearing at least onefunctional group and having 3 to 20 carbon atoms, substituted orunsubstituted aryl radical optionally interrupted by at least oneheteroatom, optionally bearing at least one functional group and having6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 5 to 18 carbon atoms and/orheteroatoms

R¹¹, R¹², R¹³, R¹⁴ are each independently hydrogen, substituent withdonor or acceptor action, linear or branched alkyl radical optionallyinterrupted by at least one heteroatom, optionally bearing at least onefunctional group and having 1 to 20 carbon atoms. cycloalkyl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 3 to 20 carbon atoms, substitutedor unsubstituted aryl radical optionally interrupted by at least oneheteroatom, optionally bearing at least one functional group and having6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 5 to 18 carbon atoms and/orheteroatoms,

or

R¹¹ and R¹² or R¹² and R¹³ and/or R¹³ and R¹⁴ together form a saturated,unsaturated or aromatic carbon ring optionally interrupted by at leastone heteroatom and having a total of 5 to 30 carbon atoms and/orheteroatoms

and/or

R¹ and R¹⁴ together form a saturated or unsaturated, linear or branchedbridge optionally comprising heteroatoms, aromatic units, heteroaromaticunits and/or functional groups and having a total of 1 to 30 carbonatoms and/or heteroatoms, to which a substituted or unsubstituted. five-to eight-membered ring comprising carbon atoms and/or heteroatoms,preferably a six-membered aromatic ring, is optionally fused, and/or

if A¹ is C, R⁷ and R⁸ together form a saturated or unsaturated, linearor branched bridge optionally comprising heteroatoms, aromatic units,heteroaromatic units and/or functional groups and having a total of 1 to30 carbon atoms and/or heteroatoms, to which a substituted orunsubstituted, five- to eight-membered ring comprising carbon atomsand/or heteroatoms, preferably a six-membered aromatic ring, isoptionally fused.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a crystal structure of Em1-s.

FIG. 2 depicts a crystal structure of Em1-i.

FIG. 3 depicts a crystal structure of Em2-i.

DETAILED DESCRIPTION

In the context of the present invention, the terms aryl radical, unit orgroup, heteroaryl radical, unit or group, alkyl radical, unit or groupand cycloalkyl radical, unit or group are each defined as follows, aslong as no different meanings are mentioned:

An aryl radical or group is understood to mean a radical with a baseskeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, whichis formed from an aromatic ring or a plurality of fused aromatic rings.Suitable base skeletons are, for example, phenyl, benzyl, naphthyl,anthracenyl or phenanthrenyl. This base skeleton may be unsubstituted,which means that all carbon atoms which are substitutable bear hydrogenatoms, or may be substituted at one, more than one or all substitutablepositions of the base skeleton. Suitable substituents are, for example,alkyl radicals, preferably alkyl radicals having 1 to 8 carbon atoms,more preferably methyl, ethyl, i-propyl or t-butyl, aryl radicals,preferably C₆-aryl radicals, which may in turn be substituted orunsubstituted, heteroaryl radicals, preferably heteroaryl radicals whichcomprise at least one nitrogen atom, more preferably pyridyl radicals,alkenyl radicals, preferably alkenyl radicals which bear one doublebond, more preferably alkenyl radicals with one double bond and 1 to 8carbon atoms, or groups with donor or acceptor action. Groups with donoraction are understood to mean groups which have a +I and/or +M effect,and groups with acceptor action are understood to mean groups which havea −I and/or −M effect. Suitable groups with donor or acceptor action arehalogen radicals, preferably F, Cl, Br, more preferably F, alkylradicals, alkoxy radicals, aryloxy radicals, carbonyl radicals, esterradicals, amine radicals, amide radicals, CH₂F groups, CHF₂ groups, CF₃groups, CN groups, thio groups or SCN groups. The aryl radicals mostpreferably bear substituents selected from the group consisting ofmethyl, ethyl. iso-propyl, n-propyl, n-butyl, iso-butyl, tert-butyl,aryloxy, amine, thio groups and alkoxy, or the aryl radicals areunsubstituted. The aryl radical or the aryl group is preferably aC₆-aryl radical optionally substituted by at least one of theaforementioned substituents. The C₆-aryl radical more preferably hasnone, one, two or three of the aforementioned substituents.

A heteroaryl radical or a heteroaryl group is understood to meanradicals having 5 to 30 carbon atoms and/or heteroatoms, which differfrom the aforementioned aryl radicals in that at least one carbon atomin the base skeleton of the aryl radicals is replaced by a heteroatom.Preferred heteroatoms are N, O and S. Most preferably, one or two carbonatoms of the base skeleton of the aryl radicals are replaced byheteroatoms. The base skeleton is especially preferably selected fromelectron-poor systems such as pyridyl. pyrimidyl, pyrazyl and triazolyl,and five-membered heteroaromatics such as pyrrole, furan, thiophene,imidazole, pyrazole, triazole, oxazole and thiazole. The base skeletonmay be substituted at one, more than one or all substitutable positionsof the base skeleton. Suitable substituents are the same as have alreadybeen specified above for the aryl groups.

An alkyl radical or an alkyl group is understood to mean a radicalhaving 1 to 20 carbon atoms. preferably 1 to 10 carbon atoms, morepreferably 1 to 8 carbon atoms. This alkyl radical may be branched orunbranched and may optionally be interrupted by one or more heteroatoms,preferably N, O or S. In addition, this alkyl radical may be substitutedby one or more of the substituents already specified for the arylgroups. It is likewise possible that the alkyl radical bears one or morearyl groups. All of the aryl groups listed above are suitable.Particular preference is given to the alkyl radicals selected from thegroup consisting of methyl, ethyl, i-propyl, n-propyl, i-butyl, n-butyl,t-butyl, sec-butyl, i-pentyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl,i-hexyl and sec-hexyl. Very particular preference is given to methyl,i-propyl, tert-butyl.

A cycloalkyl radical or a cycloalkyl group is understood to mean acyclic radical having 3 to 20 carbon atoms, preferably 3 to 10 carbonatoms, more preferably 3 to 8 carbon atoms. This cycloalkyl radical mayoptionally be interrupted by one or more heteroatoms, preferably N, O orS. In addition, this cycloalkyl radical may be unsubstituted orsubstituted, i.e. may be substituted by one or more of the substituentsalready specified for the aryl groups. It is likewise possible that thecycloalkyl radical bears one or more aryl groups. All of the aryl groupslisted above are suitable.

The statements made for the aryl, heteroaryl, alkyl and cycloalkylradicals applies, in accordance with the invention, independently to theradicals mentioned in the present application, especially to the R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ radicals, whereR⁸ and R⁹, in the case that A¹ and/or A² is N. are a free electron pair,which means that no substituent selected from the abovementioned groupis present on these ring nitrogen atoms. In the case that A¹ and/or A²is C, R and R⁹ are each independently hydrogen and/or the substituentsspecified.

In a preferred embodiment, M, A¹, A², n, m, R¹, R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are each defined as follows:According to the invention, M is Ir or Pt, preferably Ir. Ir is presentin the inventive heteroleptic complexes in the +3 oxidation state. Pt ispresent in the inventive heteroleptic complexes in the +2 oxidationstate.

According to the invention, A¹ and A² are each independently C or N.Preference is given in accordance with the invention to the followingembodiments:

-   -   1. Both A¹ and A² are C, i.e. the inventive heteroleptic        complexes comprise at least one phenylimidazole unit attached        via a metal-carbene bond.    -   2. In a further preferred embodiment, A¹ and A² are each N or C,        where A¹=N when A²=C or A¹=C when A² is N, i.e. one of A¹ and A²        is N, the other is C. In this embodiment, the inventive        heteroleptic complexes comprise at least one phenyltriazole unit        attached via a metal-carbene bond.

n and m are each independently 1 or 2, where, if M is Pt, the sum of nand m is 2, or, if M is Ir, the sum of n and m is 3. Therefore, if M isPt, n and m are each 1. If M is Ir, preferably, n=2 and m=1.

In a preferred embodiment, R¹ is a linear or branched alkyl radicalhaving 1 to 20 carbon atoms, a substituted or unsubstituted aryl radicalhaving 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylradical having 5 to 18 carbon atoms and/or heteroatoms.

R¹ is more preferably a substituted or unsubstituted aryl radical having6 to 30 carbon atoms, most preferably a substituted, especiallyortho,ortho′- or ortho,ortho′,para-substituted, or unsubstituted phenylradical. The substituents are preferably alkyl radicals having 1 to 10,especially 1 to 6, carbon atoms, for example methyl, ethyl, propyl,butyl. Very particularly preferred R¹ radicals are phenyl,2,6-dimethylphenyl, 2,6-di-iso-propylphenyl or 2,4,6-trimethylphenyl,i.e. mesityl.

The present invention therefore relates more particularly to aninventive heteroleptic complex where R¹ is an aryl radical which has 6to 30 carbon atoms and is substituted in the ortho,ortho′ positions ineach case by a linear or branched alkyl radical having 1 to 10 carbonatoms.

In a preferred embodiment, R², R³ are each independently hydrogen, alinear or branched alkyl radical having 1 to 20 carbon atoms, asubstituted or unsubstituted aryl radical having 6 to 30 carbon atoms, asubstituted or unsubstituted heteroaryl radical having 5 to 18 carbonatoms and/or heteroatoms.

In a preferred embodiment, R⁴, R⁵, R⁶, R⁷ are each hydrogen or R⁴ and R⁵or R⁵ and R⁶ or R⁶ and R⁷, especially R⁵ and R⁶ or R⁶ and R⁷, togetherform a saturated, unsaturated or aromatic carbon ring optionallyinterrupted by at least one heteroatom and having a total of 6 to 30carbon atoms.

In a very particularly preferred embodiment of the inventiveheteroleptic complex, R⁴ and R⁵ or R⁵ and R⁶ or R⁶ and R⁷ together forma cycle of the general formula (IIa) or (IIb)

In a further preferred embodiment, R⁸, R⁹ are each independently a freeelectron pair if A¹ or A² is N, or, if A¹ or A² is C, hydrogen or linearor branched alkyl radical having 1 to 20 carbon atoms, substituted orunsubstituted aryl radical having 6 to 30 carbon atoms or substituted orunsubstituted heteroaryl radical having 5 to 18 carbon atoms and/orheteroatoms, most preferably phenyl radical.

In a preferred embodiment, R¹⁰ is a linear or branched alkyl radicalhaving 1 to 20 carbon atoms, more preferably having 1 to 6 carbon atoms,or a substituted or unsubstituted aryl radical having 6 to 30 carbonatoms, more preferably having 6 to 10 carbon atoms. Examples ofparticularly preferred alkyl radicals for R¹⁰ are methyl, ethyl, propyl,especially isopropyl, butyl, especially tert-butyl, or pentyl. Examplesof particularly preferred aryl radicals for R¹⁰ are unsubstituted phenylor substituted phenyl, preferably substituted in the ortho position, forexample by alkyl radicals having 1 to 6 carbon atoms, for examplemethyl, ethyl or propyl, especially isopropyl.

In a preferred embodiment, R¹¹, R¹², R¹³, R¹⁴ are each independentlyhydrogen or a linear or branched alkyl radical having 1 to 20 carbonatoms, more preferably hydrogen.

In a further embodiment of the inventive heteroleptic complexes, R¹ andR¹⁴ together form a saturated or unsaturated, linear or branched bridgeoptionally comprising heteroatoms, aromatic units, heteroaromatic unitsand/or functional groups and having a total of 1 to 30 carbon atomsand/or heteroatoms, to which a substituted or unsubstituted, five- toeight-membered ring comprising carbon atoms and/or heteroatoms,preferably a six-membered aromatic ring, is optionally fused. Mostpreferably, R¹ and R¹⁴ form an unsaturated bridge having two carbonatoms, to which a six-membered aromatic ring is fused, which is eitherunsubstituted or substituted by one or two alkyl radicals having 1 to 6carbon atoms, for example methyl or ethyl.

In a further embodiment of the inventive heteroleptic complexes, if A¹is C, R^(T) and Re together form a saturated or unsaturated, linear orbranched bridge optionally comprising heteroatoms, aromatic units,heteroaromatic units and/or functional groups and having a total of 1 to30 carbon atoms and/or heteroatoms, to which a substituted orunsubstituted, five- to eight-membered ring comprising carbon atomsand/or heteroatoms, preferably a six-membered aromatic ring, isoptionally fused. Most preferably, R⁷ and R⁸ form an unsaturated bridgehaving two carbon atoms, to which a six-membered aromatic ring is fused,which is either unsubstituted or substituted by one or two alkylradicals having 1 to 6 carbon atoms, for example methyl or ethyl.

The present invention more preferably relates to inventive heterolepticcomplexes of the general formula (I) where M, A¹, A², n, m, R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are each defined asfollows:

-   -   M is Ir,    -   A¹, A² is C,    -   n, m are each independently 1 or 2, where the sum of n and m is        3; preferably, n=2 and m=1,    -   R¹ is a linear or branched alkyl radical having 1 to 20 carbon        atoms, substituted or unsubstituted aryl radical having 6 to 30        carbon atoms, substituted or unsubstituted heteroaryl radical        having 5 to 18 carbon atoms and/or heteroatoms; preferably R¹ is        an unsubstituted or substituted aryl radical,    -   R², R³ are each independently hydrogen, linear or branched alkyl        radical having 1 to 20 carbon atoms, substituted or        unsubstituted aryl radical having 6 to 30 carbon atoms,        substituted or unsubstituted heteroaryl radical having 5 to 18        carbon atoms and/or heteroatoms; preferably R² and R³ are each        hydrogen,    -   R⁴, R⁵,    -   R⁶, R⁷ are each hydrogen        -   or    -   R⁴ and R⁵ or R⁵ and R⁶ or R⁶ and R⁷ together form a saturated,        unsaturated or aromatic ring optionally interrupted by at least        one heteroatom and having a total of 5 to 30 carbon atoms and/or        heteroatoms,    -   R⁸, R⁹ are each hydrogen,    -   R¹⁰ is a linear or branched alkyl radical having 1 to 20 carbon        atoms, substituted or unsubstituted aryl radical having 6 to 30        carbon atoms, and    -   R¹¹, R¹²,    -   R¹³, R¹⁴ are each independently hydrogen or linear or branched        alkyl radical having 1 to 20 carbon atoms,    -   and/or    -   R¹ and R¹⁴ together form a saturated or unsaturated, linear or        branched bridge optionally comprising heteroatoms, aromatic        units, heteroaromatic units and/or functional groups and having        a total of 1 to 30 carbon atoms and/or heteroatoms, to which a        substituted or unsubstituted, five- to eight-membered ring        comprising carbon atoms and/or heteroatoms, preferably a        six-membered aromatic ring, is optionally fused,    -   and/or    -   R⁷ and R⁸ together form a saturated or unsaturated, linear or        branched bridge optionally comprising heteroatoms, aromatic        units, heteroaromatic units and/or functional groups and having        a total of 1 to 30 carbon atoms and/or heteroatoms, to which a        substituted or unsubstituted, five- to eight-membered ring        comprising carbon atoms and/or heteroatoms, preferably a        six-membered aromatic ring, is optionally fused.

The abovementioned preferred and particularly preferred embodimentsapply correspondingly.

The present invention preferably further relates to inventiveheteroleptic complexes of the general formula (I) where M, A¹, A², n, m,R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are eachdefined as follows:

-   -   M is Ir,    -   A¹, A² are each N or C, where A¹=N when A²=C and A¹=C when A²=N    -   n, m are each independently 1 or 2, where the sum of n and m is        3; preferably n=2 and m=1,    -   R¹ is a linear or branched alkyl radical having 1 to 20 carbon        atoms, substituted or unsubstituted aryl radical having 6 to 30        carbon atoms, substituted or unsubstituted heteroaryl radical        having 5 to 18 carbon atoms and/or heteroatoms; preferably R¹ is        a substituted or unsubstituted aryl radical,    -   R², R³ are each independently hydrogen, linear or branched alkyl        radical having 1 to 20 carbon atoms, substituted or        unsubstituted aryl radical having 6 to 30 carbon atoms,        substituted or unsubstituted heteroaryl radical having 5 to 18        carbon atoms and/or heteroatoms; preferably, R² and R³ are each        hydrogen,    -   R⁴, R⁵,    -   R⁶, R⁷ are each hydrogen    -   or    -   R⁴ and R⁵ or R⁵ and R⁶ or R⁶ and R⁷ together form a saturated,        unsaturated or aromatic ring optionally interrupted by at least        one heteroatom and having a total of 5 to 30 carbon atoms and/or        heteroatoms,    -   R⁸, R⁹ are each independently a free electron pair if A¹ or A²        is N, or, if A¹ or A² is C, hydrogen, linear or branched alkyl        radical having 1 to 20 carbon atoms, substituted or        unsubstituted aryl radical having 6 to 30 carbon atoms,        substituted or unsubstituted heteroaryl radical having 5 to 18        carbon atoms and/or heteroatoms,    -   R¹⁰ linear or branched alkyl radical having 1 to 20 carbon        atoms, substituted or unsubstituted aryl radical having 6 to 30        carbon atoms, and    -   R¹¹, R¹²,    -   R¹³, R¹⁴ hydrogen or linear or branched alkyl radical having        1-20 carbon atoms    -   and/or    -   R¹ and R¹⁴ together form a saturated or unsaturated, linear or        branched bridge optionally comprising heteroatoms, aromatic        units, heteroaromatic units and/or functional groups and having        a total of 1 to 30 carbon atoms and/or heteroatoms, to which a        substituted or unsubstituted, five- to eight-membered ring        comprising carbon atoms and/or heteroatoms, preferably a        six-membered aromatic ring, is optionally fused.    -   and/or    -   R^(T) and R^(o) together form a saturated or unsaturated, linear        or branched bridge optionally comprising heteroatoms, aromatic        units, heteroaromatic units and/or functional groups and having        a total of 1 to 30 carbon atoms and/or heteroatoms, to which a        substituted or unsubstituted, five- to eight-membered ring        comprising carbon atoms and/or heteroatoms, preferably a        six-membered aromatic ring, is optionally fused.

The abovementioned preferred and particularly preferred embodimentsapply correspondingly.

The present invention preferably also relates to inventive heterolepticcomplexes of the general formula (I) where M, A¹, A², n, m, R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are each defined asfollows:

-   -   M is Ir,    -   A¹ is C.    -   A² is N or C,    -   n, m are each independently 1 or 2, where the sum of n and m is        3; preferably n=2 and m=1,    -   R¹ is a linear or branched alkyl radical having 1 to 20 carbon        atoms, substituted or unsubstituted aryl radical having 6 to 30        carbon atoms, substituted or unsubstituted heteroaryl radical        having 5 to 18 carbon atoms and/or heteroatoms; preferably, R¹        is a substituted or unsubstituted aryl radical,    -   R², R³ are each independently hydrogen, linear or branched alkyl        radical having 1 to 20 carbon atoms, substituted or        unsubstituted aryl radical having 6 to 30 carbon atoms,        substituted or unsubstituted heteroaryl radical having 5 to 18        carbon atoms and/or heteroatoms; preferably R² and R³ are each        hydrogen,    -   R⁴, R⁵,    -   R⁶ are each independently hydrogen, linear or branched alkyl        radical having 1 to 20 carbon atoms, substituted or        unsubstituted aryl radical having 6 to 30 carbon atoms,    -   R⁷, R⁸ together form an unsaturated C₂ bridge, to which a        substituted or unsubstituted, five- to eight-membered ring        comprising carbon atoms and/or heteroatoms, may be fused,    -   R⁹ is a free electron pair if A² is N or, if A² is C, hydrogen,        linear or branched alkyl radical having 1 to 20 carbon atoms,        substituted or unsubstituted aryl radical having 6 to 30 carbon        atoms, substituted or unsubstituted heteroaryl radical having 5        to 18 carbon atoms and/or heteroatoms,    -   R¹⁰ is a linear or branched alkyl radical having 1 to 20 carbon        atoms, substituted or unsubstituted aryl radical having 6 to 30        carbon atoms, and    -   R¹¹, R¹²    -   R¹³, R¹⁴ are each independently hydrogen or linear or branched        alkyl radical having 1 to 20 carbon atoms,    -   and/or    -   R¹ and R¹⁴ together form a saturated or unsaturated, linear or        branched bridge optionally comprising heteroatoms, aromatic        units, heteroaromatic units and/or functional groups and having        a total of 1 to 30 carbon atoms and/or heteroatoms, to which a        substituted or unsubstituted, five- to eight-membered ring        comprising carbon atoms and/or heteroatoms, preferably a        six-membered aromatic ring, is optionally fused.

The latter embodiment corresponds to the following general formula (Ib):

Very particularly preferred inventive heteroleptic complexes of thegeneral formula (I) have the ligands depicted in table 1, especiallypreferably in the combinations shown:

TABLE 1 Ligands

K1

K2

K3

K4

K5

K6

K7

K8

K9

K10

K11

K12

K13

K14

K15

K16

K17

K18

K19

K20

K21

K22

K23

K24

K25

K26

K27

K28

K29

K30

K31

K32

K33

K34

K35

K36

K37

K38

K39

K40

K41

K42

K43

K44

K45

K46

K47

K48

K49

K50

K51

K52

K53

K54

K55

K56

K57

K58

K59

K60

K61

K62

K63

K64

K65

K66

K67

K68

K69

K70

K71

K72

K73

K74

K75

K76

K77

K78

K79

K80

K81

K82

K83

K84

K85

K86

K87

K88

K89

K90

K91

K92

K93

K94

K95

K96

In each case where M=Ir, n=2 and m=1.

Depending on the coordination number of the metal M present in theinventive heteroleptic complexes of the general formula (I) and thenumber of carbene ligands and noncarbene ligands used, different isomersof the corresponding heteroleptic metal complexes may be present withthe same metal M and the same nature of the carbene ligands andnoncarbene ligands used.

For example, for octahedral iridium(III) complexes with two noncarbeneligands and one carbene ligand, the following isomers S1 to S4 arepossible, each of which may be present in the form of two enantiomers (aand b):

In the present application, owing to the arrangement of the two2-phenyl-1H-imidazole ligands, the S1a/S1b and S2a/S2b isomers arereferred to as pseudo-meridional isomers and the S3a/S3b and S4a/S4bisomers as pseudo-facial isomers.

It has been found in accordance with the invention that, surprisingly,the S3 and S4 isomers, when used in OLEDs, give particularly goodresults with regard to efficiency and lifetime when used in diodes. TheS3a/S3b and S4a/S4b isomers, i.e. the pseudo-facial isomers, aretherefore particularly preferred in accordance with the invention. Morepreferably, the inventive complexes of the general formula (I) whichcomprise two noncarbene ligands and one carbene ligand are present aspseudo-facial isomers.

For iridium(III) complexes with one noncarbene ligand and two carbeneligands, the following isomers T1 to T4 are possible, each of which mayin turn be present in the form of two enantiomers (a and b):

In the present application, owing to the arrangement of the twophenylcarbene ligands, the T1a/T1b and T2a/T2b isomers are referred toas pseudo-meridional isomers and the T3a/T3b and T4a/T4b isomers aspseudo-facial isomers.

It has been found in accordance with the invention that, surprisingly,the T3 and T4 isomers, when used in OLEDs, usually give particularlygood results with regard to efficiency and lifetime when used in diodes.The T3a/T3b and T4a/T4b isomers, i.e. the pseudo-facial isomers, aretherefore particularly preferred in accordance with the invention. Morepreferably, the inventive complexes of the general formula (I) whichcomprise one noncarbene ligand and two carbene ligands are present aspseudo-facial isomers.

In the case of square-planar platinum(II) complexes with one carbeneligand and one noncarbene ligand, the two isomers U1 and U2 arepossible:

In general, the different isomers of the heteroleptic metal complexes ofthe formula (I) can be separated by processes known to those skilled inthe art, for example by chromatography, sublimation or crystallization.The different isomers can generally be interconverted by suitablereaction conditions (e.g. pH), thermally or photochemically.

The present invention relates both to the individual isomers orenantiomers of the heteroleptic complexes of the formula (I) and tomixtures of different isomers or enantiomers in any desired mixingratio.

The present invention therefore relates, in a particularly preferredembodiment, to the inventive heteroleptic complexes with the general andpreferred definitions specified for M, A¹, A², n, m, R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴, where these have one of thefollowing configurations IIIa, IIIb, IVa or IVb:

The present invention additionally also relates to a process forpreparing an inventive heteroleptic complex of the general formula (I)by contacting at least one precursor compound comprising the metal M andthe at least one ligand which, in the complexes of the general formula(I), is attached to M via noncarbene bonds with at least one ligandwhich, in the complexes of the general formula (I), is attached to M viaat least one carbene bond, or the ligand precursor thereof, for examplea corresponding imidazolium salt,

or

by contacting at least one precursor compound comprising the metal M anda ligand which, in the complexes of the general formula (I), is bondedto M via at least one carbene bond with at least one ligand which, inthe complexes of the general formula (I), is attached to M vianoncarbene bonds.

In a preferred embodiment of the process according to the invention, acomplex comprising appropriate noncarbene ligands, attached to theappropriate metal M, preferably iridium, and appropriate carbeneligands, preferably in deprotonated form as the free carbene or in theform of a protected carbene, for example as the silver-carbene complex,are contacted. Suitable precursor compounds comprise the appropriatesubstituents R¹ to R¹⁴ which are to be present in the complexes of thegeneral formula (I).

Appropriate complexes comprising appropriate noncarbene ligands attachedto the appropriate metal M, preferably iridium, are known to thoseskilled in the art. In addition to the noncarbene ligands present in thecomplex of the general formula (I), these complexes used as precursorcompounds may comprise further ligands known to those skilled in theart, for example halides, preferably chloride. Further suitable ligandsare, for example 1,5-cyclooctadiene (COD), phosphines, cyanides,alkoxides, pseudohalides and/or alkyl.

Particularly preferred complexes comprising appropriate noncarbeneligands, attached to the appropriate metal M, are, for example,compounds of the general formula (VI)

with the abovementioned definitions of R¹, R², R³, R¹¹, R¹², R¹³ undR¹⁴, where Y may independently be F, Cl, Br, I, methoxy or carboxylate.

Particularly preferred precursor compounds for the carbene ligands usedin complexes of the general formula (I) correspond, for example, to thegeneral formulae (VII) or (VIII)

with the abovementioned definitions of R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ andA, where Z may be F, Cl, Br, I, BF₄, PF₆, ClO₄ or SbF₆.

The carbene ligand precursors are deprotonated, preferably before thereaction, for example, by basic compounds known to those skilled in theart, for example basic metalates, basic metal acetates, acetylacetonatesor alkoxides, or bases such as KO^(t)Bu, NaO^(t)Bu, LiO^(t)Bu, NaH,silylamides, Ag₂O and phosphazene bases. In a further preferredembodiment, the carbene can also be released by removing volatilesubstances, for example lower alcohols such as methanol, ethanol, forexample at elevated temperature and/or reduced pressure, from precursorcompounds of the carbene ligands. Corresponding processes are known tothose skilled in the art.

The contacting is preferably effected in a solvent. Suitable solventsare known to those skilled in the art and are preferably selected fromthe group consisting of aromatic or aliphatic solvents, for examplebenzene or toluene, cyclic or acyclic ethers, alcohols, esters, amides,ketones, nitriles, halogenated compounds and mixtures thereof.Particularly preferred solvents are toluene, xylenes, dioxane and THF.

The molar ratio of metal-noncarbene complex used to carbene ligandprecursor used is generally 1:10 to 10:1, preferably 1:1 to 1:5, morepreferably 1:2 to 1:4.

The contacting is generally effected at a temperature of 20 to 200° C.,preferably 50 to 150° C., more preferably 60 to 130° C.

The reaction time depends on the desired carbene complex and isgenerally 0.02 to 50 hours, preferably 0.1 to 24 hours, more preferably1 to 12 hours.

The complexes of the general formula (I) obtained after the reaction canoptionally be purified by processes known to those skilled in the art,for example washing, crystallization or chromatography, and optionallyisomerized under conditions likewise known to those skilled in the art,for example thermally or photochemically.

The aforementioned heteroleptic complexes and mixtures thereof areoutstandingly suitable as emitter molecules in organic light-emittingdiodes (OLEDs). Variations in the ligands make it possible to providecorresponding complexes which exhibit electroluminescence in the red,green and especially in the blue region of the electromagnetic spectrum.The inventive heteroleptic complexes of the general formula (I) aretherefore outstandingly suitable as emitter substances, since they haveemission (electroluminescence) in the visible region of theelectromagnetic spectrum, for example at 400 to 800 nm, preferably 400to 600 nm. The inventive heteroleptic complexes make it possible toprovide compounds which have electroluminescence in the red, green andespecially in the blue region of the electromagnetic spectrum. It isthus possible, with the aid of the inventive heteroleptic complexes asemitter substances, to provide industrially usable OLEDs.

Further the inventive heteroleptic complexes of the general formula (I)are suitable as matrix material, charge transport material, especiallyhole transport material, and/or charge blocker material.

The inventive heteroleptic complex of the general formula (I) arepreferably suitable as emitter and/or hole transport material, morepreferably as emitter.

Particular properties of the inventive heteroleptic complexes of thegeneral formula (I) are particularly good efficiencies and lifetimeswhen used in OLEDs.

The present application therefore further provides an OLED comprising atleast one inventive heteroleptic complex of the general formula (I). Theinventive heteroleptic complex of the general formula (I) is preferablyemployed in the OLED as emitter, matrix material, charge transportmaterial, especially hole transport material, and/or hole blocker, morepreferably as emitter and/or hole transport material, particularlypreferably as emitter.

The present application also provides for the use of the heterolepticcomplexes of the general formula (I) as a light-emitting layer in OLEDs,preferably as an emitter, matrix material, charge transport material,especially hole transport material, and/or charge blocker, morepreferably as emitter and/or hole transport material, particularlypreferably as emitter.

Organic light-emitting diodes are in principle formed from a pluralityof layers:

-   -   anode (1)    -   hole-transporting layer (2)    -   light-emitting layer (3)    -   electron-transporting layer (4)    -   cathode (5).

However, it is also possible, that the OLED does not comprise all of thelayers mentioned, an OLED formed from the layers (1) (anode), (3)(light-emitting layer) and (5) (cathode) is for example also useful,wherein the functions of the layers (2) (hole-transport layer) and (4)(electron-transporting layer) are taken over by the adjacent layers.OLEDs comprising the layers (1), (2), (3) and (5) respectively thelayers (1), (3), (4) and (5) are also suitable.

The heteroleptic complexes of the general formula (I) are preferablyused as emitter molecules and/or matrix materials in the light-emittinglayer (3). The inventive heteroleptic complexes of the general formula(I) can also be employed—in addition to the application as emittermolecules and/or matrix materials in the light-emitting layer (3) orinstead of the application in the light-emitting layer—as chargetransport material in the hole-transporting layer (2) or in theelectron-transporting layer (4) and/or as charge blocker, wherein theapplication as charge transport material in the hole-transporting layer(2) (hole-transport material) is preferred.

The present application therefore further provides a light-emittinglayer comprising at least one of the inventive heteroleptic complexes ofthe general formula (I), preferably as emitter molecule. Preferredheteroleptic complexes of the general formula (I) have already beenspecified above.

The heteroleptic complexes of the general formula (I) used in accordancewith the invention may be present in the light-emitting layer insubstance, i.e. without further additions. However, it is also possiblethat, in addition to the heteroleptic complexes of the general formula(I) used in accordance with the invention, further compounds are presentin the light-emitting layer. For example, a fluorescent dye may bepresent in order to alter the emission color of the heteroleptic complexused as the emitter molecule. In addition, a diluent material (matrixmaterial) may be used. This diluent material may be a polymer, forexample poly(N-vinylcarbazole) or polysilane. The diluent material may,however, likewise be a small molecule, for example4,4′-N,N′-dicarbazolebiphenyl (CDP) or tertiary aromatic amines. When adiluent material is used, the proportion of the inventive heterolepticcomplexes of the general formula (I) used in the light-emitting layer isgenerally less than 40% by weight, preferably 3 to 30% by weight. Theinventive heteroleptic complexes of the general formula (I) arepreferably used in a matrix. The light-emitting layer thus preferablycomprises at least one inventive heteroleptic complex of the generalformula (I) and at least one matrix material as diluent material.

Suitable matrix materials are—in addition to the aforementioned dilutionmaterials—in principle the materials specified hereinafter as hole andelectron transport materials, and also carbene complexes, for examplethe carbene complexes of the formula (I) or the carbene complexesmentioned in WO 2005/019373. Particularly suitable are carbazolederivatives, for example 4,4′-bis(carbazol-9-yl)-2,2′-dimethylbiphenyl(CDBP), 4,4′-bis(carbazol-9-yl)biphenyl (CBP),1,3-bis(N-carbazolyl)benzene (mCP), and the matrix materials specifiedin the following applications: WO2008/034758, WO2009/003919.

Further suitable matrix materials, which may be small molecules or(co)polymers of the small molecules mentioned, are specified in thefollowing publications:

WO2007108459 (H-1 to H-37), preferably H-20 to H-22 and H-32 to H-37,most preferably H-20, H-32, H-36, H-37, WO2008035571 A1 (Host 1 to Host6), JP2010135467 (compounds 1 to 46 and Host-1 to Host-39 and Host-43),WO2009008100 compounds No. 1 to No. 67, preferably No. 3, No. 4, No. 7to No. 12, No. 55, No. 59, No. 63 to No. 67, more preferably No. 4, No.8 to No. 12, No. 55, No. 59, No. 64, No. 65, and No. 67, WO2009008099compounds No. 1 to No. 110, WO2008140114 compounds 1-1 to 1-50,WO2008090912 compounds OC-7 to OC-36 and the polymers of Mo-42 to Mo-51,JP2008084913 H-1 to H-70, WO2007077810 compounds 1 to 44, preferably 1,2, 4-6, 8, 19-22, 26, 28-30, 32, 36, 39-44, WO201001830 the polymers ofmonomers 1-1 to 1-9, preferably of 1-3, 1-7, and 1-9, WO2008029729 the(polymers of) compounds 1-1 to 1-36, WO20100443342 HS-1 to HS-101 andBH-1 to BH-17, preferably BH-1 to BH-17, JP2009182298 the (co)polymersbased on the monomers 1 to 75, JP2009170764, JP2009135183 the(co)polymers based on the monomers 1-14, WO2009063757 preferably the(co)polymers based on the monomers 1-1 to 1-26, WO2008146838 thecompounds a-1 to a-43 and 1-1 to 1-46, JP2008207520 the (co)polymersbased on the monomers 1-1 to 1-26, JP2008066569 the (co)polymers basedon the monomers 1-1 to 1-16, WO2008029652 the (co)polymers based on themonomers 1-1 to 1-52, WO2007114244 the (co)polymers based on themonomers 1-1 to 1-18, JP2010040830 the compounds HA-1 to HA-20, HB-1 toHB-16, HC-1 to HC-23 and the (co)polymers based on the monomers HD-1 toHD-12, JP2009021336, WO2010090077 the compounds 1 to 55, WO2010079678the compounds H1 to H42, WO2010067746, WO2010044342 the compounds HS-1to HS-101 and Poly-1 to Poly-4, JP2010114180 the compounds PH-1 toPH-36, US2009284138 the compounds 1 to 111 and H1 to H71, WO2008072596the compounds 1 to 45, JP2010021336 the compounds H-1 to H-38,preferably H-1, WO2010004877 the compounds H-1 to H-60, JP2009267255 thecompounds 1-1 to 1-105, WO2009104488 the compounds 1-1 to 1-38,WO2009086028, US2009153034, US2009134784, WO2009084413 the compounds 2-1to 2-56, JP2009114369 the compounds 2-1 to 2-40, JP2009114370 thecompounds 1 to 67, WO2009060742 the compounds 2-1 to 2-56, WO2009060757the compounds 1-1 to 1-76, WO2009060780 the compounds 1-1 to 1-70,WO2009060779 the compounds 1-1 to 1-42, WO2008156105 the compounds 1 to54, JP2009059767 the compounds 1 to 20, JP2008074939 the compounds 1 to256, JP2008021687 the compounds 1 to 50, WO2007119816 the compounds 1 to37, WO2010087222 the compounds H-1 to H-31, WO2010095564 the compoundsHOST-1 to HOST-61, WO2007108362, WO2009003898, WO2009003919,WO2010040777, US2007224446 and WO06128800.

In a particularly preferred embodiment, one or more compounds of thegeneral formula (X) specified hereinafter are used as matrix material.Preferred embodiments of the compounds of the general formula (X) arelikewise specified hereinafter.

The matrix materials mentioned above as well as the compounds of thegeneral formula (X) mentioned below are not only applicable as matrixmaterial in the light-emitting layer, but also as matrix materials inother layers of an OLED, for example in the electron-transport layerand/or in the hole transport layer. It is also possible, to apply two ormore different matrix materials mentioned before and/or compounds of thegeneral formula (X) mentioned below as matrix materials.

In order to obtain particularly efficient OLEDs, the HOMO (highestoccupied molecular orbital) of the hole-transporting layer should bealigned to the work function of the anode, and the LUMO (lowestunoccupied molecular orbital) of the electron-transporting layer shouldbe aligned to the work function of the cathode.

The present application further provides an OLED comprising at least oneinventive light-emitting layer. The further layers in the OLED may beformed from any material which is typically used in such layers and isknown to those skilled in the art.

Suitable materials for the aforementioned layers (anode, cathode, holeand electron injection materials, hole and electron transport materialsand hole and electron blocker materials, matrix materials, fluorescenceand phosphorescence emitters) are known to those skilled in the art andare specified, for example, in H. Meng, N. Herron, Organic SmallMolecule Materials for Organic Light-Emitting Devices in OrganicLight-Emitting Materials and Devices, eds: Z. Li, H. Meng, Taylor &Francis, 2007, Chapter 3, pages 295 to 411.

The anode is an electrode which provides positive charge carriers. Itmay be composed, for example, of materials which comprise a metal, amixture of different metals, a metal alloy, a metal oxide or a mixtureof different metal oxides. Alternatively, the anode may be a conductivepolymer. Suitable metals comprise the metals of groups 11, 4, 5 and 6 ofthe Periodic Table of the Elements, and also the transition metals ofgroups 8 to 10. When the anode is to be transparent, mixed metal oxidesof groups 12, 13 and 14 of the Periodic Table of the Elements aregenerally used, for example indium tin oxide (ITO). It is likewisepossible that the anode (1) comprises an organic material, for examplepolyaniline, as described, for example, in Nature, Vol. 357, pages 477to 479 (Jun. 11, 1992). At least either the anode or the cathode shouldbe at least partly transparent in order to be able to emit the lightformed.

Suitable hole transport materials for layer (2) of the inventive OLEDare disclosed, for example, in Kirk-Othmer Encyclopedia of ChemicalTechnology, 4th Edition, Vol. 18, pages 837 to 860, 1996. Eitherhole-transporting molecules or polymers may be used as the holetransport material. Customarily used hole-transporting molecules areselected from the group consisting of4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD),N,N′-diphenyl-N,N′-bis(3-methylphenyt)-[1,1′-biphenyl]-4,4′-diamine(TPD), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC),N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD), tetrakis(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA),α-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehydediphenylhydrazone (DEH), triphenylamine (TPA),bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP),1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)-cyclobutane (DCZB),N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB),fluorene compounds such as 2,2′, 7,7′-tetra(N,N-di-tolyl)amino-9,9-spirobifluorene (spiro-TTB), N,N′-bis(naphthalene-1-yl)-N, N′-bis(phenyl)-9,9-spirobifluorene(spiro-NPB) and9,9-bis(4-(N,N-bis-biphenyl-4-yl-amino)phenyl-9H-fluorene, benzidinecompounds such as N,N′-bis(naphthalene-1-yl)-N,N′-bis(phenyl)benzidineand porphyrin compounds such as copper phthalocyanines. Customarily usedhole-transporting polymers are selected from the group consisting ofpolyvinylcarbazoles, (phenylmethyl)polysilanes and polyanilines. It islikewise possible to obtain hole-transporting polymers by dopinghole-transporting molecules into polymers such as polystyrene andpolycarbonate. Suitable hole-transporting molecules are the moleculesalready mentioned above.

In addition—in one embodiment—it is possible to use carbene complexes ashole conductor materials, in which case the band gap of the at least onehole conductor material is generally greater than the band gap of theemitter material used. In the context of the present invention, band gapis understood to mean the triplet energy. Suitable carbene complexesare, for example, the inventive carbene complexes of the general formula(I), carbene complexes as described in WO 2005/019373 A2, WO 2006/056418A2, WO 2005/113704, WO 2007/115970, WO 2007/115981 and WO 2008/000727.One example of a suitable carbene complex is Ir(DPBIC)₃ with theformula:

It is likewise possible to use mixtures in the hole-transporting layer,in particular mixtures which lead to electrical p-doping of thehole-transporting layer. p-Doping is achieved by the addition ofoxidizing materials. These mixtures may, for example, be the followingmixtures: mixtures of the abovementioned hole transport materials withat least one metal oxide, for example MoO₂, MoO₃, WO_(x), ReO₃, and/orpreferably MoO₃ and/or ReO₃, more preferably ReO₃ or mixtures comprisingthe aforementioned hole transport materials and one or more compoundsselected from V₂O₅, 7,7,8,8-tetracyanoquinodimethane (TCNQ),2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F₄-TCNQ),2,5-bis(2-hydroxyethoxy)-7,7,8,8-tetracyanoquinodimethane,bis(tetra-n-butylammonium)tetracyanodiphenoquino-dimethane,2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene,11,11,12,12-tetracyanonaphtho-2,6-quinodimethane,2-fluoro-7,7,8,8-tetracyanoquino-dimethane,2,5-difluoro-7,7,8,8-tetracyanoquinodimethane,dicyanomethylene-1,3,4,5,7,8-hexafluoro-6H-naphthalen-2-ylidene)malononitrile(Fe-TNAP), Mo(tfd)₃ (from Kahn et al., J. Am. Chem. Soc. 2009, 131 (35),12530-12531), compounds as mentioned in EP 1 988 587 and in EP 2 180 029and with quinone compounds as mentioned in EP 09153776.1.

Suitable electron-transporting materials for layer (4) of the inventiveOLEDs comprise metals chelated with oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (Alq₃), compounds based onphenanthroline such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline(DDPA=BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen),4,7-diphenyl-1,10-phenanthroline (DPA) or phenanthroline derivativesdisclosed in EP1786050 or in EP1097981, and azole compounds such as2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ).Layer (4) may serve both to ease the electron transport and as a bufferlayer or as a barrier layer in order to prevent quenching of the excitonat the interfaces of the layers of the OLED. Layer (4) preferablyimproves the mobility of the electrons and reduces quenching of theexciton.

It is likewise possible to use mixtures of at least two materials in theelectron-transporting layer, in which case at least one material iselectron-conducting. Preferably, in such mixed electron-transportinglayers, at least one phenanthroline compound is used. More preferably,in mixed electron-transporting layers, in addition to at least onephenanthroline compound, alkali metal hydroxyquinolate complexes, forexample Liq, are used. In addition, it is possible to use mixtures whichlead to electrical n-doping of the electron-transporting layer. n-Dopingis achieved by the addition of reducing materials. These mixtures may,for example, be mixtures of the abovementioned electron transportmaterials with alkali/alkaline earth metals or alkali/alkaline earthmetal salts, for example Li, Cs, Ca, Sr, Cs₂CO₃, with alkali metalcomplexes, for example 8-hydroxyquinolatolithium (Liq), and with Y, Ce,Sm, Gd, Tb, Er, Tm, Yb, Li₃N, Rb₂CO₃, dipotassium phthalate, W(hpp)₄from EP 1786050, or with compounds as described in EP1837926 B1.

The present invention therefore also relates to an inventive OLED whichcomprises an electron-transporting layer comprising at least twodifferent materials, of which at least one material should beelectron-conductive.

In a preferred embodiment, the present invention relates to an inventiveOLED wherein the electron-transporting layer comprises at least onephenanthroline derivative.

In a further preferred embodiment, the invention relates to an inventiveOLED wherein the electron-transporting layer comprises at least onephenanthroline derivative and at least one alkali metal hydroxyquinolatecomplex.

In a further preferred embodiment, the invention relates to an inventiveOLED wherein the electron-transporting layer comprises at least onephenanthroline derivative and 8-hydroxyquinolatolithium.

Some of the materials mentioned above as hole transport materials andelectron-transporting materials can fulfill several functions. Forexample, some of the electron-transporting materials are simultaneouslyhole-blocking materials if they have a low-lying HOMO.

The charge-transporting layers may also be electronically doped in orderto improve the transport properties of the materials used, in orderfirstly to make the layer thickness more generous (avoidance ofpinholes/short circuits) and in order secondly to minimize the operatingvoltage of the device. The hole transport materials may for example bedoped with electron acceptors, phthalocyanines respectively arylamineslike TPD or TDTA may be for example doped withtetrafluorotetracyano-chinodimethane (F4-TCNQ). Electronic doping isknown to those skilled in the art and is disclosed, for example, in W.Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1, 1. July 2003 (p-dopedorganic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz,K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 23. June 2003 and Pfeifferet al., Organic Electronics 2003, 4, 89-103 and K. Walzer, B. Maennig,M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233.

The cathode (5) is an electrode which serves to introduce electrons ornegative charge carriers. The cathode may be any metal or nonmetal whichhas a lower work function than the anode. Suitable materials for thecathode are selected from the group consisting of alkali metals of group1, for example Li, Cs, alkaline earth metals of group 2, metals of group12 of the Periodic Table of the Elements, comprising the rare earthmetals and the lanthanides and actinides. In addition, metals such asaluminum, indium, calcium, barium, samarium and magnesium, andcombinations thereof, may be used. In addition, lithium-comprisingorganometallic compounds such as 8-hydroxyquinolatolithium (Liq) or LiFor at least one of the following compounds (Cs₂CO₃, KF, CsF or NaF maybe applied between the organic layer and the cathode as an electroninjection layer in order to reduce the operating voltage.

The OLED of the present invention may additionally comprise furtherlayers which are known to those skilled in the art. For example, a layerwhich eases the transport of the positive charge and/or matches the bandgaps of the layers to one another may be applied between the layer (2)and the light-emitting layer (3). Alternatively, this further layer mayserve as a protective layer. In an analogous manner, additional layersmay be present between the light-emitting layer (3) and the layer (4) inorder to ease the transport of the negative charge and/or to match theband gaps between the layers to one another. Alternatively, this layermay serve as a protective layer.

In a preferred embodiment, the inventive OLED, in addition to the layers(1) to (5), comprises at least one of the further layers mentionedbelow:

-   -   a hole injection layer between the anode (1) and the        hole-transporting layer (2);    -   a blocking layer for electrons between the hole-transporting        layer (2) and the light-emitting layer (3);    -   a blocking layer for holes between the light-emitting layer (3)        and the electron-transporting layer (4);    -   an electron injection layer between the electron-transporting        layer (4) and the cathode (5).

As already mentioned above, however, it is also possible that the OLEDdoes not have all of the layers (1) to (5) mentioned; for example, anOLED comprising layers (1) (anode), (3) (light-emitting layer) and (5)(cathode) is likewise suitable, in which case the functions of layers(2) (hole-transporting layer) and (4) (electron-transporting layer) areassumed by the adjoining layers. OLEDs having layers (1), (2), (3) and(5) or layers (1), (3), (4) and (5) are likewise suitable.

Those skilled in the art know how suitable materials have to be selected(for example on the basis of electrochemical investigations). Suitablematerials for the individual layers are known to those skilled in theart and disclosed, for example, in WO 00/70655.

In addition, it is possible that some or all of the layers (1), (2),(3), (4) and (5) have been surface-treated in order to increase theefficiency of charge carrier transport. The selection of the materialsfor each of the layers mentioned is preferably determined by obtainingan OLED having a high efficiency.

The inventive OLED can be produced by methods known to those skilled inthe art. In general, the OLED is produced by successive vapor depositionof the individual layers onto a suitable substrate. Suitable substratesare, for example, glass, inorganic materials like ITO or IZO or polymerfilms. For the vapor deposition, customary techniques may be used, suchas thermal evaporation, chemical vapor deposition (CVD), physical vapordeposition (PVD) and others.

In an alternative process, the organic layers may be coated fromsolutions or dispersions in suitable solvents, in which case coatingtechniques known to those skilled in the art are employed.

Suitable coating techniques are, for example, spin-coating, the castingmethod, the Langmuir-Blodgett (“LB”) method, the inkjet printing method,dip-coating, letterpress printing, screen printing, doctor bladeprinting, roller printing, reverse roller printing, offset lithographyprinting, flexographic printing, web printing, spray coating, coating bya brush or pad printing, and the like. Among the processes mentioned, inaddition to the aforementioned vapor deposition, preference is given tospin-coating, the inkjet printing method and the casting method sincethey are particularly simple and inexpensive to perform. In the casethat layers of the OLED are obtained by the spin-coating method, thecasting method or the inkjet printing method, the coating can beobtained using a solution prepared by dissolving the composition in aconcentration of 0.0001 to 90% by weight in a suitable organic solventsuch as benzene, toluene, xylene, tetrahydrofuran,methyltetrahydrofuran, N,N-dimethylformamide, acetone, acetonitrile,anisole, dichloromethane, dimethyl sulfoxide, water and mixturesthereof.

It is also possible that all layers of the OLED are prepared with thesame coating technique. It is further also possible that two or morecoating techniques are carried out in the production of the layers ofthe OLED.

In general, the different layers have the following thicknesses: anode(2) 500 to 5000 Å, preferably 1000 to 2000 Å (ångström);hole-transporting layer (3) 50 to 1000 Å, preferably 200 to 800 Å;light-emitting layer (4) 10 to 1000 Å, preferably 100 to 800 Å;electron-transporting layer (5) 50 to 1000 Å, preferably 200 to 800 Å;cathode (6) 200 to 10 000 Å, preferably 300 to 5000 Å. The position ofthe recombination zone of holes and electrons in the inventive OLED andthus the emission spectrum of the OLED may be influenced by the relativethickness of each layer. This means that the thickness of the electrontransport layer should preferably be selected such that theelectron/hole recombination zone is within the light-emitting layer. Theratio of the layer thicknesses of the individual layers in the OLED isdependent upon the materials used. The layer thicknesses of anyadditional layers used are known to those skilled in the art.

In a preferred embodiment, the present invention also relates to an OLEDcomprising at least one inventive heteroleptic complex of the generalformula (I), and at least one compound of the general formula (X)

in which

-   -   T is NR⁵⁷, S, O or PR⁵⁷, preferably S or O, more preferably O;    -   R⁵⁷ is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;    -   Q′ is —NR⁵⁸R⁵⁹, —P(O)R⁶⁰R⁶¹, —PR⁶²R⁶³, —S(O)₂R⁶⁴, —S(O)R⁶⁵,        —SR⁶⁶ or —OR⁶⁷, preferably —NR⁵⁸R⁵⁹; more preferably

-   -   -   in which        -   R⁶⁸, R⁶⁹ are each independently alkyl, cycloalkyl,            heterocycloalkyl, aryl or heteroaryl; preferably methyl,            carbazolyl, dibenzofuryl or dibenzothienyl;        -   y, z are each independently 0, 1, 2, 3 or 4, preferably 0 or            1;

    -   R⁵⁵, R⁵⁶ are each independently alkyl, cycloalkyl,        heterocycloalkyl, aryl, heteroaryl, SiR⁷⁰R⁷¹R⁷², a Q′ group or a        group with donor or acceptor action;

    -   a″ is 0, 1, 2, 3 or 4;

    -   b′ is 0, 1, 2 or 3;

    -   R⁵⁸, R⁵⁹ form, together with the nitrogen atom, a cyclic radical        which has 3 to 10 ring atoms and may be unsubstituted or        substituted by one or more substituents selected from alkyl,        cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with        donor or acceptor action, and/or may be fused to one or more        further cyclic radicals having 3 to 10 ring atoms, where the        fused radicals may be unsubstituted or substituted by one or        more substituents selected from alkyl, cycloalkyl,        heterocycloalkyl, aryl, heteroaryl and a group with donor or        acceptor action;

    -   R⁷⁰, R⁷¹, R⁷², R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷

    -   are each independently aryl, heteroaryl, alkyl, cycloalkyl or        heterocycloalkyl,

    -   or

    -   two units of the general formula (X) are bridged to one another        via a linear or branched, saturated or unsaturated bridge        optionally interrupted by at least one heteroatom, via a bond or        via O.

Preference is given to compounds of the formula (X) in which:

-   -   T is S or O, preferably O, and

-   -   Q′ is    -   in which    -   R⁶⁸, R⁶⁹ are each independently alkyl, cycloalkyl,        heterocycloalkyl, aryl or heteroaryl; preferably methyl,        carbazolyl, dibenzofuryl or dibenzothienyl;    -   y, z are each independently 0, 1, 2, 3 or 4, preferably 0 or 1.

Particularly preferred compounds of the formula (X) have the followingformula (Xa):

in which the symbols and indices Q′, T, R⁵⁵, R⁵⁶, a″ and b′ are each asdefined above.

Very particularly preferred compounds of the formula (X have the formulaXaa):

in which the symbols and indices R⁶⁸, R⁶⁹ y, z, T, R⁵⁵, R⁵⁶, a″ and b′are each as defined above.

In a very particularly preferred embodiment, in formula (Xaa):

-   -   T is O or S, preferably 0;    -   a″ is 1;    -   b′ is 0;    -   y, z are each independently 0 or 1; and    -   R⁶⁸, R⁶⁹ are each independently methyl, carbazolyl, dibenzofuryl        or dibenzothienyl    -   R⁵⁵ is substituted phenyl, carbazolyl, dibenzofuryl or        dibenzothienyl.

In a further preferred embodiment, the compounds of the formula (X) havethe formula (XI) or (XI*):

in which

-   -   T is NR⁵⁷, S, O or PR⁵⁷;    -   R⁵⁷ is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;    -   Q′ is —NR⁵⁸R⁵⁹, —P(O)R⁶⁰R⁶¹, —PR⁶²R⁶³, —S(O)₂R⁶⁴, —S(O)R⁶⁵,        —SR⁶⁶ or —OR⁶⁷;    -   R⁷⁰, R⁷¹, R⁷² are each independently aryl, heteroaryl, alkyl,        cycloalkyl, heterocycloalkyl, where at least one of the R⁷⁰,        R⁷¹, R⁷² radicals comprises at least two carbon atoms, or OR⁷³,    -   R⁵⁵, R⁵⁶ are each independently alkyl, cycloalkyl,        heterocycloalkyl, aryl, heteroaryl, a Q group or a group with        donor or acceptor action;    -   a′, b′ for the compound of the formula (XI): are each        independently 0, 1, 2, 3; for the compound of the formula (XI*),        a′ is 0, 1, 2 and b′ is 0, 1, 2, 3, 4;    -   R⁵⁸, R⁵⁹ form, together with the nitrogen atom, a cyclic radical        which has 3 to 10 ring atoms and may be unsubstituted or        substituted by one or more substituents selected from alkyl,        cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with        donor or acceptor action and/or may be fused to one or more        further cyclic radicals having 3 to 10 ring atoms, where the        fused radicals may be unsubstituted or substituted by one or        more substituents selected from alkyl, cycloalkyl,        heterocycloalkyl, aryl, heteroaryl and a group with donor or        acceptor action;    -   R⁷³ are each independently SiR⁷⁴R⁷⁵R⁷⁶, aryl, heteroaryl, alkyl,        cycloalkyl or heterocycloalkyl, optionally substituted by an        OR⁷⁷ group,    -   R⁷⁷ are each independently SiR⁷⁴R⁷⁵R⁷⁶, aryl, heteroaryl, alkyl,        cycloalkyl or heterocycloalkyl,    -   R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, R⁷⁴, R⁷⁵, R⁷⁶ are each        independently aryl, heteroaryl, alkyl, cycloalkyl or    -   heterocycloalkyl,    -   or    -   two units of the general formulae (XI) and/or (XI*) are bridged        to one another via a linear or branched, saturated or        unsaturated bridge optionally interrupted by at least one        heteroatom or via O, where this bridge in the general        formulae (XI) and/or (XI*) is in each case attached to the        silicon atoms in place of R¹.

The compounds of the general formula (X) can be used as a matrix(diluent material), hole/exciton blocker, electron/exciton blocker,electron transport material or hole transport material in combinationwith the heteroeleptic complexes claimed, which then preferably serve asemitters. Inventive OLEDs which include both at least one compound ofthe formula (X) and a compound of the formula (I) exhibit particularlygood efficiencies and lifetimes. Depending on the function in which thecompound of the formula (X) is used, it is present in pure form or indifferent mixing ratios. In a particularly preferred embodiment, one ormore compounds of the formula (X) are used as matrix material in thelight-emitting layer.

For the compounds of the general formula (X), especially for the R⁵⁵ toR⁷⁷ radicals:

The terms aryl radical or group, heteroaryl radical or group, alkylradical or group, cycloalkyl radical or group, heterocycloalkyl radicalor group, alkenyl radical or group, alkynyl radical or group, and groupswith donor and/or acceptor action are each defined as follows:

An aryl radical (or group) is understood to mean a radical having a baseskeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, whichis formed from an aromatic ring or a plurality of fused aromatic rings.Suitable base skeletons are, for example, phenyl, naphthyl, anthracenylor phenanthrenyl, indenyl or fluorenyl. This base skeleton may beunsubstituted (which means that all carbon atoms which are substitutablebear hydrogen atoms), or may be substituted at one, more than one or allsubstitutable positions of the base skeleton.

Suitable substituents are, for example, deuterium, alkoxy radicals,aryloxy radicals, alkylamino groups, arylamino groups, carbazolylgroups, silyl groups, SiR⁷⁸R⁷⁹R⁸⁰, suitable silyl groups SiR⁷⁸R⁷⁹R⁸⁰being specified below, alkyl radicals, preferably alkyl radicals having1 to 8 carbon atoms, more preferably methyl, ethyl or i-propyl, arylradicals, preferably Ce-aryl radicals, which may in turn be substitutedor unsubstituted, heteroaryl radicals, preferably heteroaryl radicalswhich comprise at least one nitrogen atom, more preferably pyridylradicals and carbazolyl radicals, alkenyl radicals, preferably alkenylradicals which bear one double bond, more preferably alkenyl radicalshaving one double bond and 1 to 8 carbon atoms, alkynyl radicals,preferably alkynyl radicals having one triple bond, more preferablyalkynyl radicals having one triple bond and 1 to 8 carbon atoms orgroups with donor or acceptor action. Suitable groups with donor oracceptor action are specified below. The substituted aryl radicals mostpreferably bear substituents selected from the group consisting ofmethyl, ethyl, isopropyl, alkoxy, heteroaryl, halogen, pseudohalogen andamino, preferably arylamino. The aryl radical or the aryl group ispreferably a C₆-C₁₈-aryl radical, more preferably a C₆-aryl radical,which is optionally substituted by at least one or more than one of theaforementioned substituents. The C₆-C₁₈-aryl radical, preferably C₆-arylradical, more preferably has none, one, two, three or four, mostpreferably none, one or two, of the aforementioned substituents.

A heteroaryl radical or a heteroaryl group is understood to meanradicals which differ from the aforementioned aryl radicals in that atleast one carbon atom in the base skeleton of the aryl radicals isreplaced by a heteroatom, and in that the base skeleton of theheteroaryl radicals preferably has 5 to 18 ring atoms. Preferredheteroatoms are N, O and S. Heteroaryl radicals suitable with particularpreference are nitrogen-containing heteroaryl radicals. Most preferably,one or two carbon atoms of the base skeleton are replaced byheteroatoms, preferably nitrogen. The base skeleton is especiallypreferably selected from systems such as pyridine, pyrimidine andfive-membered heteroaromatics such as pyrrole, furan, pyrazole,imidazole, thiophene, oxazole, thiazole, triazole. In addition, theheteroaryl radicals may be fused ring systems, for example benzofuryl,benzothienyl, benzopyrrolyl, dibenzofuryl, dibenzothienyl,phenanthrolinyl, carbazolyl radicals, azacarbazolyl radicals ordiazacarbazolyl radicals. The base skeleton may be substituted at one,more than one or all substitutable positions of the base skeleton.Suitable substituents are the same as have already been specified forthe aryl groups.

An alkyl radical or an alkyl group is understood to mean a radicalhaving 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, morepreferably 1 to 8, most preferably 1 to 4 carbon atoms. This alkylradical may be branched or unbranched and optionally be interrupted byone or more heteroatoms, preferably Si, N, O or S, more preferably N, Oor S. In addition, this alkyl radical may be substituted by one or moreof the substituents specified for the aryl groups. In addition, thealkyl radicals present in accordance with the invention may have atleast one halogen atom, for example F, CI, Br or I, especially F. In afurther embodiment, the alkyl radicals present in accordance with theinvention may be fully fluorinated. It is likewise possible that thealkyl radical bears one or more (hetero)aryl groups. In the context ofthe present application, for example, benzyl radicals are thussubstituted alkyl radicals. In this context, all of the (hetero)arylgroups listed above are suitable. The alkyl radicals are more preferablyselected from the group consisting of methyl, ethyl, isopropyl,n-propyl, n-butyl, iso-butyl and tert-butyl, very particular preferencebeing given to methyl and ethyl.

A cycloalkyl radical or a cycloalkyl group is understood to mean aradical having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms,more preferably 3 to 8 carbon atoms. This base skeleton may beunsubstituted (which means that all carbon atoms which are substitutablebear hydrogen atoms) or substituted at one, more than one or allsubstitutable positions of the base skeleton. Suitable substituents arethe groups already mentioned above for the aryl radicals. It is likewisepossible that the cycloalkyl radical bears one or more (hetero)arylgroups. Examples of suitable cycloalkyl radicals are cyclopropyl,cyclopentyl and cyclohexyl.

A heterocycloalkyl radical or a heterocycloalkyl group is understood tomean radicals which differ from the aforementioned cycloalkyl radicalsin that at least one carbon atom in the base skeleton of the cycloalkylradicals is replaced by a heteroatom. Preferred heteroatoms are N, O andS. Most preferably, one or two carbon atoms of the base skeleton of thecycloalkyl radicals are replaced by heteroatoms. Examples of suitableheterocycloalkyl radicals are radicals derived from pyrrolidine,piperidine, piperazine, tetrahydrofuran, dioxane.

An alkenyl radical or an alkenyl group is understood to mean a radicalwhich corresponds to the aforementioned alkyl radicals having at leasttwo carbon atoms, with the difference that at least one C—C single bondof the alkyl radical is replaced by a C═C double bond. The alkenylradical preferably has one or two double bonds.

An alkynyl radical or an alkynyl group is understood to mean a radicalwhich corresponds to the aforementioned alkyl radicals having at leasttwo carbon atoms, with the difference that at least one C—C single bondof the alkyl radical is replaced by a C—C triple bond. The alkynylradical preferably has one or two triple bonds.

An SiR⁷⁰R⁷⁹R⁸⁰ group is understood to mean a silyl radical in which

R⁷⁸, R⁷⁹ and R⁸⁰ are each independently alkyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl or OR⁷³.

An SiR⁷⁴R⁷⁵R⁷⁶ group is understood to mean a silyl radical in which

R⁷⁴, R⁷⁵ and R⁷⁶ are each independently alkyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl or OR⁷³.

In the context of the present application, a group or a substituent withdonor or acceptor action is understood to mean the following groups:

Groups with donor action are understood to mean groups which have a +Iand/or +M effect, and groups with acceptor action are understood to meangroups which have a −I and/or −M effect. Preferred suitable groups areselected from C₁-C₂₀-alkoxy, C₆-C₃₀-aryloxy, C₁-C₂₀-alkylthio,C₆-C₃₀-arylthio, SiR⁸¹R⁸²R⁸³, OR⁷³, halogen radicals, halogenatedC₁-C₂₀-alkyl radicals, carbonyl (—CO(R⁸¹)), carbonylthio (—C═O (SR⁸¹)),carbonyloxy (—C═O(OR⁸¹)), oxycarbonyl (—OC═O(R⁸¹)), thiocarbonyl(—SC═O(R⁸¹)) amino (—NR⁸¹R⁸²), pseudohalogen radicals, amido (—C═O(NR⁸¹)), —NR⁸¹C═O (R⁸³), phosphonate (—P(O) (OR⁸¹)₂, phosphate (—OP(O)(OR⁸¹)₂), phosphine (—PR⁸¹R⁸²), phosphine oxide (—P(O)R⁸¹ ₂), sulfate(—OS(O)₂OR⁸¹), sulfoxide (—S(O)R⁸¹), sulfonate (—S(O)₂OR⁸¹), sulfonyl(—S(O)₂R⁸¹, sulfonamide (—S(O)₂NR⁸¹R⁸²), NO₂, boronic esters(—OB(OR⁸¹)₂), imino (—C═NR⁸¹R⁸²)), borane radicals, stannane radicals,hydrazine radicals, hydrazone radicals, oxime radicals, nitroso groups,diazo groups, vinyl groups, sulfoximines, alanes, germanes, boroximesand borazines.

The R⁸¹, R⁸² and R⁸³ radicals mentioned in the aforementioned groupswith donor or acceptor action are each independently:

substituted or unsubstituted C₁-C₂₀-alkyl or substituted orunsubstituted C₆-C₃₀-aryl, or OR⁷⁶, suitable and preferred alkyl andaryl radicals having been specified above. The R⁸¹, R⁸² and R⁸³ radicalsare more preferably C₁-C₆-alkyl, e.g. methyl, ethyl or i-propyl, orphenyl. In a preferred embodiment—in the case of SiR⁸¹R⁸²R⁸³-R⁸¹, R⁸²and R⁸³ are preferably each independently substituted or unsubstitutedC₁-C₂₀-alkyl or substituted or unsubstituted aryl, preferably phenyl.

Preferred substituents with donor or acceptor action are selected fromthe group consisting of:

C₁- to C₂₀-alkoxy, preferably C₁-C₆-alkoxy, more preferably ethoxy ormethoxy; C₆-C₃₀-aryloxy, preferably C₆-C₁₀-aryloxy, more preferablyphenyloxy; SiR⁸¹R⁸²R⁸³ where R⁸¹, R⁸² and R⁸³ are preferably eachindependently substituted or unsubstituted alkyl or substituted orunsubstituted aryl, preferably phenyl; more preferably, at least one ofthe R⁸¹, R⁸² and R⁸³ radicals is substituted or unsubstituted phenyl,suitable substituents having been specified above; halogen radicals,preferably F, Cl, more preferably F, halogenated C₁-C₂₀-alkyl radicals,preferably halogenated C₁-C₆-alkyl radicals, most preferably fluorinatedC₁-C₆-alkyl radicals, e.g. CF₃, CH₂F, CHF₂ or C₂F₅; amino, preferablydimethylamino, diethylamino or diarylamino, more preferably diarylamino;pseudohalogen radicals, preferably CN, —C(O)OC₁-C₄-alkyl, preferably—C(O)OMe, P(O)R₂, preferably P(O)Ph₂.

Very particularly preferred substituents with donor or acceptor actionare selected from the group consisting of methoxy, phenyloxy,halogenated C₁-C₄-alkyl, preferably CF₃, CH₂F, CHF₂, C₂F₅, halogen,preferably F, CN, SiR⁸¹R⁸²R⁸³, suitable R⁸¹, R⁸² and R⁸³ radicalsalready having been specified, diarylamino (NR⁸⁴R⁸⁵ where R⁸⁴, R⁸⁵ areeach C₆-C₃₀-aryl), —C(O)OC₁-C₄-alkyl, preferably —C(O)OMe, P(O)Ph₂.

Halogen groups are preferably understood to mean F, Cl and Br, morepreferably F and Cl, most preferably F.

Pseudohalogen groups are preferably understood to mean CN, SCN and OCN,more preferably CN.

The aforementioned groups with donor or acceptor action do not rule outthe possibility that further radicals and substituents mentioned in thepresent application, but not included in the above list of groups withdonor or acceptor action, have donor or acceptor action.

The aryl radicals or groups, heteroaryl radicals or groups, alkylradicals or groups, cycloalkyl radicals or groups, heterocycloalkylradicals or groups, alkenyl radicals or groups and groups with donorand/or acceptor action may—as mentioned above—be substituted orunsubstituted. In the context of the present application, anunsubstituted group is understood to mean a group in which thesubstitutable atoms of the group bear hydrogen atoms. In the context ofthe present application, a substituted group is understood to mean agroup in which one or more substitutable atom(s) bear(s) a substituentin place of a hydrogen atom at least at one position. Suitablesubstituents are the substituents specified above for the aryl radicalsor groups.

When radicals having the same numbering occur more than once in thecompounds according to the present application, these radicals may eachindependently have the definitions specified.

The T radical in the compounds of the formula (X) is NR⁵⁷, S, O or PR⁵⁷,preferably NR⁵⁷, S or O, more preferably O or S, most preferably O.

The R⁵⁷ radical is aryl, heteroaryl, alkyl, cycloalkyl orheterocycloalkyl, preferably aryl, heteroaryl or alkyl, more preferablyaryl, where the aforementioned radicals may be unsubstituted orsubstituted. Suitable substituents have been specified above. R⁶⁵ ismore preferably phenyl which may be substituted by the aforementionedsubstituents or unsubstituted. R⁵⁷ is most preferably unsubstitutedphenyl.

The Q′ group in the compounds of the formula (X) is —NR⁵⁸R⁹,—P(O)R⁶⁰R⁶¹, —PR⁶²R⁶³, —S(O)₂R⁶⁴, —S(O)R⁶⁵, —SR⁶⁶ or —OR⁶⁷; preferablyNR⁵⁸R⁵⁹, —P(O)R⁶⁰R⁶¹ or —OR⁶⁷, more preferably —NR⁵⁸R⁵⁹.

The R⁵⁸ to R⁶⁷ and R⁷⁴ to R⁷⁶ radicals are each defined as follows:

-   -   R⁵⁸, R⁵⁹ form, together with the nitrogen atom, a cyclic radical        which has 3 to 10 ring atoms and may be unsubstituted or        substituted by one or more substituents selected from alkyl,        cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with        donor or acceptor action and/or may be fused to one or more        further cyclic radicals having 3 to 10 ring atoms, where the        fused radicals may be unsubstituted or substituted by one or        more substituents selected from alkyl, cycloalkyl,        heterocycloalkyl, aryl, heteroaryl and a group with donor or        acceptor action;    -   R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, R⁷⁴, R⁷⁵, R⁷⁶    -   are each independently aryl, heteroaryl, alkyl, cycloalkyl or        heterocycloalkyl, preferably aryl or heteroaryl, where the        radicals may be unsubstituted or substituted by one or more of        the radicals selected from alkyl, cycloalkyl, heterocycloalkyl,        aryl, heteroaryl and a group with donor or acceptor action, more        preferably unsubstituted or substituted phenyl, suitable        substituents having been specified above, for example tolyl or a        group of the formula

-   -   in which the T group and the R⁷⁰, R⁷¹ and R⁷² radicals are each        independently as defined for the compounds of the formula (XI)        or (XI*).    -   R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶ and R⁸⁷ are most preferably        each independently phenyl, tolyl or a group of the formula

in which T is NPh, S or O.

Examples of —NR⁵⁸R⁵⁹ groups suitable with preference are selected fromthe group consisting of pyrrolyl, 2,5-dihydro-1-pyrrolyl, pyrrolidinyl,indolyl, indolinyl, isoindolinyl, carbazolyl, azacarbazolyl,diazacarbazolyl, imidazolyl, imidazolinyl, benzimidazolyl, pyrazolyl,indazolyl, 1,2,3-triazolyl, benzotriazolyl, 1,2,4-triazolyl, tetrazolyl,1,3-oxazolyl, 1,3-thiazolyl, piperidyl, morpholinyl,9,10-dihydroacridinyl and 1,4-oxazinyl, where the aforementioned groupsmay be unsubstituted or substituted by one or more substituents selectedfrom alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a groupwith donor or acceptor action; the —NR⁶R⁷ group is preferably selectedfrom carbazolyl, pyrrolyl, indolyl, imidazolyl, benzimidazolyl,azacarbazolyl and diazacarbazolyl, where the aforementioned groups maybe unsubstituted or substituted by one or more substituents selectedfrom alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a groupwith donor or acceptor action; the —NR⁵⁸R⁵⁹ group is more preferablycarbazolyl which may be unsubstituted or substituted by one or moresubstituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl,heteroaryl and a group with donor or acceptor action.

Particularly preferred—NR⁵⁸R⁵⁹ groups are:

in which

-   -   R⁶⁸, R⁶⁹ are each independently alkyl, cycloalkyl,        heterocycloalkyl, aryl or heteroaryl; preferably methyl,        carbazolyl, dibenzofuryl or dibenzothienyl;    -   y, z are each independently 0, 1, 2, 3 or 4, preferably 0 or 1;    -   for example:

-   -   in which X is NPh, S or O;

-   -   in which X is NPh, S or O,

Particularly preferred—P(O)R⁶⁰R⁶¹ groups are:

A particularly preferred PR⁶²R⁶³ group is:

Particularly preferred groups —S(O)₂R⁶⁴ and —S(O)R⁶⁵ are:

Particularly preferred groups —SR⁶⁶ and —OR⁶⁷ are:

-   -   in which T is in each case NPh, S or O.

R⁵⁵, R⁵⁶ in the compounds of the formula (X) are each independentlyalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, a further A groupor a group with donor or acceptor action; preferably each independentlyalkyl, aryl, heteroaryl or a group with donor or acceptor action. Forexample, R⁵⁵ or R⁵⁶ may each independently be:

-   -   in which X is NPh, S or O.

In the compounds of the formula (X) a″ R⁵⁵ groups and/or b′ R⁵⁶ groupsmay be present, where a″ and b′ are:

a″ is 0, 1, 2, 3 or 4; preferably independently 0, 1 or 2;

b′ is 0, 1, 2 or 3; preferably independently 0, 1 or 2.

Most preferably at least a″ or b′ is 0, very especially preferably a″and b′ are each 0 or a″ is 1 and b′ is 0.

R⁷³ in the compounds of the general formula (XI) is generallyindependently SiR⁷⁴R⁷⁵R⁷⁶, aryl, heteroaryl, alkyl, cycloalkyl orheterocycloalkyl, optionally substituted by an OR group.

R⁷⁷ in compounds of the general formula (XI) is generally independentlyaryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl.

The OR⁷⁷ substituent optionally present may generally be present in theradicals mentioned at all sites which appear suitable to the personskilled in the art.

In a further embodiment, two units of the general formula (XI) and/or(XI*) are bridged to one another via a linear or branched, saturated orunsaturated bridge optionally interrupted by at least one heteroatom orvia O, where this bridge in the general formula (XI) and/or (XI*) is ineach case attached to the silicon atoms in place of R⁷¹.

This bridge is preferably selected from the group consisting of —CH₂—,—C₂H₄—, —C₃H₆—, —C₄H₈—, —C₆H₁₂—, —C₈H₁₈—, —C₉H₁₈—, —CH(C₈H₁₇)CH₂,—C₂H₄(CF₂)₈ C₂H₄—, —C≡C—, −1,4-(CH₂)₂-phenyl-(CH₂)—,1,3-(CH₂)₂-phenyl-(CH₂)₂—, −1,4-phenyl-, −1,3-phenyl-, —O—,—O—Si(CH₃)₂—O—, —O—Si(CH₃)—O— Si(CH₃)₂—O—, —O—.

In a preferred embodiment of the present application, the compounds ofthe general formula (X) have the general formula (XIa), (XIb), (XIc),(XId) or (XIe), i.e. they are preferred embodiments of the compounds ofthe general formula (XI) or (XI*):

in which the Q′, T, R⁷⁰, R⁷¹, R⁷², R⁵⁵, R⁵⁶ radicals and groups, and a′and b′, are each as defined above.

In another embodiment preferred in accordance with the invention, R⁷⁰,R⁷¹ or R⁷² in the compounds of the general formula (XI) or (XI*) arearomatic units of the general formulae (Xli) and/or (Xli*)

where R⁵⁵, R⁵⁶, Q′, T, a′ and b′ are each as defined above.

The present invention therefore relates, in one embodiment, to aninventive OLED where R⁷⁰, R⁷¹ or R⁷² in the compounds of the generalformula (XI) or (XI*) are aromatic units of the general formulae (XIi)and/or (XIi*)

where R⁵⁶, R⁵⁶, Q′, T, a′ and b′ are each as defined above.

In a preferred embodiment, the present invention relates to an OLEDwherein the compound of the general formula (XI) or (XI*) is selectedfrom the following group:

In these particularly preferred compounds of the general formula (XI) or(XI*):

-   -   T is S or O, and    -   R′ is H or CH₃; and    -   R⁷⁰, R⁷¹, R⁷² are each phenyl, carbazolyl, dibenzofuran or        dibenzothiophene.

Further particularly suitable compounds of the general formula XI or XI*are:

In these particularly preferred compounds of the general formula (XI) or(XI*) too, T is O or S, preferably O.

Further inventive compounds of the general formula (XI) or (XI′)correspond to the following formula (XII)

In the general formula (XII), R⁷⁰, R⁷¹, R⁷² are each defined as follows:

Nr R⁷⁰ R⁷¹ R⁷²   1 methyl methyl ethyl   2 methyl methyl i-propyl   3methyl methyl n-propyl   4 methyl methyl n-butyl   5 methyl methyli-butyl   6 methyl methyl t-butyl   7 methyl methyl n-pentyl   8 methylmethyl n-hexyl   9 methyl methyl —CH₂CH₂C(CH₃)₃  10 methyl methyln-C₈H₁₇  11 methyl methyl i-C₈H₁₇  12 methyl methyl n-C₁₀H₂₁  13 methylmethyl n-C₁₂H₂₅  16 methyl methyl n-C₁₈H₃₇  17 methyl methyl n-C₃₀H₆₁ 19 methyl methyl cyclohexyl  20 methyl methyl C(CH₃)₂Ph  21 methylmethyl —C(CH₃)₂CH(CH₃)₂  22 methyl methyl —CCH₂CH(CH₃)(C₂H₅)  23 methylmethyl —CH₂CH(C₁₀H₂₁)₂  24 methyl methyl —CH₂CH(C₁₂H₂₅)₂  25 methylmethyl —CH₂CH₂(C₃F₆)CF₃  26 methyl methyl —CH₂CH₂(C₇F₁₄)CF₃  27 methylmethyl —CH₂CH₂(C₅F₁₀)CF₃  29 methyl methyl —CH₂CH₂CF₃  30 methyl methylphenyl  31 methyl methyl 2-biphenyl  32 methyl methyl p-tolyl  33 methylmethyl C₆F₅  34 methyl methyl 3,5-(cf₃)₂phenyl  35 methyl methyl—ch₂c(ch₃)₂phenyl  36 methyl methyl 9-fluorenyl  37 methyl methyl3,6-di(tert-butyl)-9-fluorenyl  15 methyl methyl R⁸⁶  38 methyl methyl—OMe  39 methyl methyl —OEt  40 methyl methyl 2,4,6-t-butylphenoxy  41methyl methyl —O-tBu (tert-butoxy)  42 methyl methyl —OSiEt₃  43 methylethyl ethyl  44 methyl ethyl phenyl  45 methyl ethyl R⁸⁶  46 methyln-propyl n-propyl  47 methyl n-propyl phenyl  48 methyl n-propyl R⁸⁶  49methyl i-propyl i-propyl  50 methyl i-propyl phenyl  51 methyl i-propylR⁸⁶  52 methyl n-butyl n-butyl  53 methyl n-butyl phenyl  54 methyln-butyl R⁸⁶  55 methyl i-butyl i-butyl  56 methyl i-butyl phenyl  57methyl i-butyl R⁸⁶  58 methyl t-butyl t-butyl  59 methyl t-butyl phenyl 60 methyl t-butyl R⁸⁶  61 methyl n-pentyl n-Pentyl  62 methyl n-pentyln-hexyl  63 methyl n-pentyl phenyl  64 methyl n-pentyl R⁸⁶  65 methyln-hexyl hexyl  66 methyl n-hexyl phenyl  67 methyl n-hexyl R⁸⁶  68methyl n-heptyl R⁸⁶  69 methyl n-octyl R⁸⁶  70 methyl n-decyl R⁸⁶  71methyl n-C₁₂H₂₅ R⁸⁶  72 methyl n-C₁₈H₃₇ R⁸⁶  73 methyl n-C₂₂H₄₅ R⁸⁶  74methyl n-C₃₀H₆₁ R⁸⁶  75 methyl cyclopentyl cyclopentyl  76 methylcyclopentyl phenyl  77 methyl cyclopentyl R⁸⁶  78 methyl cyclohexylcyclohexyl  79 methyl cyclohexyl phenyl  80 methyl cyclohexyl R⁸⁶  81methyl —CF₂CHF₂ R⁸⁶  82 methyl —CH₂CH₂CF₃ R⁸⁶  83 methyl—CH₂CH₂(CF₂)₃CF₃ R⁸⁶  84 methyl —CH₂CH₂(CF₂)₅CF₃ R⁸⁶  85 methyl—CH₂CH₂(CF₂)₇CF₃ R⁸⁶  86 methyl phenyl phenyl  87 methyl phenyl p-tolyl 89 methyl phenyl mesityl  90 methyl phenyl R⁸⁶  91 methyl p-tolylp-tolyl  92 methyl p-tolyl R⁸⁶  93 methyl mesityl mesityl  94 methylmesityl R5  95 methyl R⁸⁶ R⁸⁶  96 methyl methoxy methoxy  97 methylethoxy ethoxy  98 methyl —OSiEt₃ —OSiEt₃  99 methyl—O—SiMe₂—CH₂CH₂(CF₂)₄CF₃ —O—SiMe₂-CH₂CH₂(CF₂)₄CF₃ 100 ethyl ethyl ethyl101 ethyl ethyl n-propyl 102 ethyl ethyl i-propyl 103 ethyl ethyln-butyl 104 ethyl ethyl i-butyl 105 ethyl ethyl t-butyl 106 ethyl ethylphenyl 107 ethyl ethyl R5 108 ethyl phenyl phenyl 109 ethyl phenyl R⁸⁶110 ethyl R⁸⁶ R⁸⁶ 111 ethyl ethoxy ethoxy 112 n-propyl n-propyl n-propyl113 n-propyl n-propyl phenyl 114 n-propyl n-propyl R⁸⁶ 115 n-propylphenyl phenyl 116 n-propyl phenyl R⁸⁶ 117 n-propyl R⁸⁶ R⁸⁶ 118 i-propyli-propyl i-propyl 119 i-propyl i-propyl phenyl 120 i-propyl i-propyl R⁸⁶121 i-propyl i-propyl 2-biphenyl 122 i-propyl i-propyl ethoxy 123i-propyl phenyl phenyl 124 i-propyl phenyl R⁸⁶ 125 i-propyl R⁸⁶ R⁸⁶ 126n-butyl n-butyl n-butyl 127 n-butyl n-butyl phenyl 128 n-butyl n-butylR⁸⁶ 129 n-butyl n-hexyl R⁸⁶ 130 n-butyl phenyl phenyl 131 n-butyl phenylR⁸⁶ 132 n-butyl R⁸⁶ R⁸⁶ 133 sec-butyl sec-butyl sec-butyl 134 sec-butylsec-butyl phenyl 135 sec-butyl sec-butyl R⁸⁶ 136 sec-butyl phenyl phenyl137 sec-butyl phenyl R⁸⁶ 138 sec-butyl R⁸⁶ R⁸⁶ 139 i-butyl i-butyli-butyl 140 i-butyl i-butyl n-C₈H₁₇ 141 i-butyl i-butyl n-C₁₈H₃₇ 142i-butyl i-butyl phenyl 143 i-butyl i-butyl R⁸⁶ 144 i-butyl phenyl phenyl145 i-butyl phenyl R⁸⁶ 146 i-butyl R⁸⁶ R⁸⁶ 147 t-butyl t-butyl t-butyl148 t-butyl t-butyl n-C₈H₁₇ 149 t-butyl t-butyl phenyl 150 t-butylt-butyl R⁸⁶ 151 t-butyl phenyl phenyl 152 t-butyl phenyl R5 153 t-butylR⁸⁶ R⁸⁶ 154 n-pentyl n-pentyl n-pentyl 155 n-pentyl n-pentyl phenyl 156n-pentyl n-pentyl R⁸⁶ 157 n-pentyl phenyl phenyl 158 n-pentyl phenyl R⁸⁶159 n-pentyl R⁸⁶ R⁸⁶ 160 cyclopentyl cyclopentyl cyclopentyl 161cyclopentyl cyclopentyl phenyl 162 cyclopentyl cyclopentyl R⁸⁶ 163cyclopentyl phenyl phenyl 164 cyclopentyl phenyl R⁸⁶ 165 cyclopentyl R⁸⁶R⁸⁶ 166 n-hexyl n-hexyl n-hexyl 167 n-hexyl n-hexyl phenyl 168 n-hexyln-hexyl R⁸⁶ 169 n-hexyl phenyl phenyl 170 n-hexyl phenyl R⁸⁶ 171 n-hexylR⁸⁶ R⁸⁶ 172 —CH₂CH₂C(CH₃)₃ —CH₂CH₂C(CH₃)₃ —CH₂CH₂C(CH₃)₃ 173—CH₂CH₂C(CH₃)₃ —CH₂CH₂C(CH₃)₃ R⁸⁶ 174 —CH₂CH₂C(CH₃)₃ R⁸⁶ R⁸⁶ 175 t-hexylt-hexyl t-hexyl 176 t-hexyl t-hexyl R⁸⁶ 177 t-hexyl R⁸⁶ R⁸⁶ 178 n-heptyln-heptyl n-heptyl 179 n-heptyl n-heptyl R⁸⁶ 180 n-heptyl R⁸⁶ R⁸⁶ 181n-octyl n-octyl n-octyl 182 n-octyl n-octyl R⁸⁶ 183 n-octyl R⁸⁶ R⁸⁶ 184i-octyl i-octyl i-octyl 185 i-octyl i-octyl R⁸⁶ 186 i-octyl R⁸⁶ R⁸⁶ 187n-nonyl n-nonyl n-nonyl 188 n-nonyl n-nonyl R⁸⁶ 189 n-nonyl R⁸⁶ R⁸⁶ 190cyclohexyl cyclohexyl cyclohexyl 191 cyclohexyl cyclohexyl R⁸⁶ 192cyclohexyl R⁸⁶ R⁸⁶ 193 cyclooctyl cyclooctyl cyclooctyl 194 cyclooctylcyclooctyl R⁸⁶ 195 cyclooctyl R⁸⁶ R⁸⁶ 196 n-C₁₀H₂₁ n-C₁₀H₂₁ n-C₁₀H₂₁ 197n-C₁₀H₂₁ n-C₁₀H₂₁ R⁸⁶ 198 n-C₁₀H₂₁ R⁸⁶ R⁸⁶ 199 n-C₁₁H₂₃ n-C₁₁H₂₃n-C₁₁H₂₃ 200 n-C₁₁H₂₃ n-C₁₁H₂₃ R⁸⁶ 201 n-C₁₁H₂₃ R⁸⁶ R⁸⁶ 202 n-C₁₂H₂₅n-C₁₂H₂₅ n-C₁₂H₂₅ 203 n-C₁₂H₂₅ n-C₁₂H₂₅ R⁸⁶ 204 n-C₁₂H₂₅ R⁸⁶ R⁸⁶ 205n-C₁₄H₂₉ n-C₁₄H₂₉ n-C₁₄H₂₉ 206 n-C₁₄H₂₉ n-C₁₄H₂₉ R⁸⁶ 207 n-C₁₄H₂₉ R⁸⁶R⁸⁶ 208 n-C₁₆H₃₃ n-C₁₆H₃₃ n-C₁₆H₃₃ 209 n-C₁₆H₃₃ n-C₁₆H₃₃ R⁸⁶ 210n-C₁₆H₃₃ R⁸⁶ R⁸⁶ 211 n-C₁₈H₃₇ n-C₁₈H₃₇ R⁸⁶ 212 n-C₁₈H₃₇ R⁸⁶ R⁸⁶ 213n-C₁₈H₃₇ OEt OEt 214 n-C₁₈H₃₇ R⁸⁶ OMe 215 n-C₂₀H₄₁ n-C₂₀H₄₁ n-C₂₀H₄₁ 216n-C₂₀H₄₁ n-C₂₀H₄₁ R⁸⁶ 217 n-C₂₀H₄₁ R⁸⁶ R⁸⁶ 218 n-C₂₂H₄₅ n-C₂₂H₄₅n-C₂₂H₄₅ 219 n-C₂₂H₄₅ n-C₂₂H₄₅ R⁸⁶ 220 n-C₂₂H₄₅ R⁸⁶ R⁸⁶ 221 n-C₂₆H₅₃n-C₂₆H₅₃ n-C₂₆H₅₃ 222 n-C₂₆H₅₃ n-C₂₆H₅₃ R⁸⁶ 223 n-C₂₆H₅₃ R⁸⁶ R⁸⁶ 224n-C₃₀H₆₁ n-C₃₀H₆₁ n-C₃₀H₆₁ 225 n-C₃₀H₆₁ n-C₃₀H₆₁ R⁸⁶ 226 n-C₃₀H₆₁ R⁸⁶R⁸⁶ 227 —CH₂-cyclohexyl —CH₂-cyclohexyl R⁸⁶ 228 —CH₂CH₂CF₃ —CH₂CH₂CF₃—CH₂CH₂CF₃ 229 —CH₂CH₂CF₃ —CH₂CH₂CF₃ R⁸⁶ 230 —CH₂CH₂CF₃ R⁸⁶ R⁸⁶ 231—CH₂CH₂(CF₂)₃CF₃ —CH₂CH₂(CF₂)₃CF₃ —CH₂CH₂(CF₂)₃CF₃ 232 —CH₂CH₂(CF₂)₃CF₃—CH₂CH₂(CF₂)₃CF₃ R⁸⁶ 233 —CH₂CH₂(CF₂)₃CF₃ R⁸⁶ R⁸⁶ 234 —CH₂CH₂(CF₂)₅CF₃—CH₂CH₂(CF₂)₅CF₃ —CH₂CH₂(CF₂)₅CF₃ 235 —CH₂CH₂(CF₂)₅CF₃ —CH₂CH₂(CF₂)₅CF₃R⁸⁶ 236 —CH₂CH₂(CF₂)₅CF₃ R⁸⁶ R⁸⁶ 237 —CH₂CH₂(CF₂)₇CF₃ —CH₂CH₂(CF₂)₇CF₃—CH₂CH₂(CF₂)₇CF₃ 238 —CH₂CH₂(CF₂)₇CF₃ —CH₂CH₂(CF₂)₇CF₃ R⁸⁶ 239—CH₂CH₂(CF₂)₇CF₃ R⁸⁶ R⁸⁶ 240 —CH₂CH₂(CF₂)₉CF₃ —CH₂CH₂(CF₂)₉CF₃—CH₂CH₂(CF₂)₉CF₃ 241 —CH₂CH₂(CF₂)₉CF₃ —CH₂CH₂(CF₂)₉CF₃ R⁸⁶ 242—CH₂CH₂(CF₂)₉CF₃ R⁸⁶ R⁸⁶ 243 —CH₂CH₂(CF₂)₁₁CF₃ —CH₂CH₂(CF₂)₁₁CF₃—CH₂CH₂(CF₂)₁₁CF₃ 244 —CH₂CH₂(CF₂)₁₁CF₃ —CH₂CH₂(CF₂)₁₁CF₃ R⁸⁶ 245—CH₂CH₂(CF₂)₁₁CF₃ R⁸⁶ R⁸⁶ 246 —CF₂CHF₂ —CF₂CHF₂ —CF₂CHF₂ 247 —CF₂CHF₂—CF₂CHF₂ R⁸⁶ 248 —CF₂CHF₂ R⁸⁶ R⁸⁶ 249 —(CF₂)₃CHF₂ —(CF₂)₃CHF₂—(CF₂)₃CHF₂ 250 —(CF₂)₃CHF₂ —(CF₂)₃CHF₂ R⁸⁶ 251 —(CF₂)₃CHF₂ R⁸⁶ R⁸⁶  14phenyl phenyl phenyl 252 phenyl phenyl p-tolyl 253 phenyl phenyl m-tolyl254 phenyl phenyl o-tolyl 255 phenyl phenyl 2-xylyl 256 phenyl phenyl5-xylyl 257 phenyl phenyl mesityl 258 phenyl phenyl 9-fluorenyl  18phenyl phenyl R⁸⁶ 259 phenyl phenyl —O-tBu (tert-butoxy) 260 phenylp-tolyl p-tolyl 261 phenyl m-tolyl m-tolyl 262 phenyl o-tolyl o-tolyl263 phenyl 2-xylyl 2-xylyl 264 phenyl 5-xylyl 5-xylyl 265 phenyl mesitylmesityl 266 phenyl R⁸⁶ R⁸⁶ 267 phenyl ethoxy ethoxy 268 p-tolyl p-tolylp-tolyl 269 p-tolyl p-tolyl R⁸⁶ 270 p-tolyl R⁸⁶ R⁸⁶ 271 m-tolyl m-tolylm-tolyl 272 m-tolyl m-tolyl R⁸⁶ 273 o-tolyl o-tolyl o-tolyl 274 o-tolylo-tolyl R⁸⁶ 275 2-xylyl 2-xylyl 2-xylyl 276 2-xylyl 2-xylyl R⁸⁶ 2775-xylyl 5-xylyl 5-xylyl 278 5-xylyl 5-xylyl R⁸⁶ 279 mesityl mesitylmesityl 280 mesityl mesityl R⁸⁶ 281 C₆F₅ C₆F₅ C₆F₅ 282 C₆F₅ C₆F₅ R⁸⁶ 283C₆F₅ R⁸⁶ R⁸⁶ 284 R⁸⁶ R⁸⁶ R⁸⁶ 285 R⁸⁶ ethoxy ethoxy 286 R⁸⁶ n-butoxyn-butoxy 287 R⁸⁶ R⁸⁶ methoxy 288 R⁸⁶ R⁸⁶ ethoxy 289 R⁸⁶ R⁸⁶ osime₃ 290R⁸⁶ R⁸⁶ —(CH₂)₁₁O—(CH₂)₂OCH₃ 291 methoxy methoxy methoxy 292 ethoxyethoxy ethoxy 293 i-propoxy i-propoxy i-propoxy 294 t-butoxy t-butoxyt-butoxy 295 OSiMe₃ OSiMe₃ osime₃ 296 cyclobutyl methyl 297 cyclobutylR⁸⁶ 298 cyclobutyl p-methoxyphenyl 299 cyclopentyl methyl 300cyclopentyl R⁸⁶ 301 cyclohexyl methyl 302 cyclohexyl R⁸⁶

In this table,

Particularly preferred compounds in which two units of the generalformulae (XI) and/or (XI*) are bridged to one another via a linear orbranched, saturated or unsaturated bridge optionally interrupted by atleast one heteroatom or via O, where this bridge in the general formulae(XI) and/or (XI*) is in each case attached to the silicon atoms in placeof R⁷¹, correspond to the general formula (XIII)

In formula (XIII), U, R⁷⁰, R⁷¹, R⁷², R⁸⁷, R⁸⁸ and R⁸⁹ are each definedas follows:

Nr. R70 R71 R72 R87 R88 R89 U 303 methyl R⁸⁶ R⁸⁶ methyl R5 R⁸⁶ —CH₂— 304methyl methyl R⁸⁶ methyl methyl R⁸⁶ —CH₂— 305 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶—CH₂— 306 methyl R⁸⁶ R⁸⁶ methyl R5 R⁸⁶ —C₂H₄— 307 methyl methyl R⁸⁶methyl methyl R⁸⁶ —C₂H₄— 308 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ —C₂H₄— 309 methylR⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶ —C₃H₆— 310 methyl methyl R⁸⁶ methyl methyl R⁸⁶—C₃H₆— 311 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ —C₃H₆— 312 methyl R⁸⁶ R⁸⁶ methyl R⁸⁶R⁸⁶ —C₄H₈— 313 methyl methyl R⁸⁶ methyl methyl R⁸⁶ —C₄H₈— 314 R⁸⁶ R⁸⁶R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ —C₄H₈— 315 methyl R⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶ —C₆H₁₂— 316methyl methyl R⁸⁶ methyl methyl R⁸⁶ —C₆H₁₂— 317 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶—C₆H₁₂— 318 methyl R⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶ —C₈H₁₆— 319 methyl methyl R⁸⁶methyl methyl R⁸⁶ —C₈H₁₆— 320 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ —C₈H₁₆— 321 methylR⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶ —C₉H₁₈— 322 methyl methyl R⁸⁶ methyl methyl R⁸⁶—C₉H₁₈— 323 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ —C₉H₁₈— 324 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶—CH(C₈H₁₇)CH₂— 325 methyl R⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶ —C₂H₄(CF₂)₈C₂H₄— 326methyl methyl R⁸⁶ methyl methyl R⁸⁶ —C₂H₄(CF₂)₈C₂H₄— 327 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶R⁸⁶ R⁸⁶ —C₂H₄(CF₂)₈C₂H₄— 328 methyl R⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶ —C≡C— 329methyl methyl R⁸⁶ methyl methyl R⁸⁶ —C≡C— 330 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶—C≡C— 331 methyl R⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶ -1,4-(CH₂)₂-phenyl-(CH₂)₂— 332methyl methyl R⁸⁶ methyl methyl R⁸⁶ -1,4-(CH₂)₂-phenyl-(CH₂)₂— 333 R⁸⁶R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ -1,4-(CH₂)₂-phenyl-(CH₂)₂— 334 methyl R⁸⁶ R⁸⁶ methylR⁸⁶ R⁸⁶ -1,3-(CH₂)₂-phenyl-(CH₂)₂— 335 methyl methyl R⁸⁶ methyl methylR⁸⁶ -1,3-(CH₂)₂-phenyl-(CH₂)₂— 336 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶-1,3-(CH₂)₂-phenyl-(CH₂)₂— 337 methyl R⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶-1,4-(CH₂)₃-phenyl-(CH₂)₃— 338 methyl methyl R⁸⁶ methyl methyl R⁸⁶-1,4-(CH₂)₃-phenyl-(CH₂)₃— 339 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶-1,4-(CH₂)₃-phenyl-(CH₂)₃— 340 methyl R⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶-1,3-(CH₂)₃-phenyl-(CH₂)₃— 341 methyl methyl R⁸⁶ methyl methyl R⁸⁶-1,3-(CH₂)₃-phenyl-(CH₂)₃— 342 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶-1,3-(CH₂)₃-phenyl-(CH₂)₃— 343 methyl R⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶-1,4-phenyl- 344 methyl methyl R⁸⁶ methyl methyl R⁸⁶ -1,4-phenyl- 345R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ -1,4-phenyl- 346 methyl R⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶-1,3-phenyl- 347 methyl methyl R⁸⁶ methyl methyl R⁸⁶ -1,3-phenyl- 348R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ -1,3-phenyl-  28 methyl methyl R⁸⁶ methyl methylR⁸⁶ —O— 349 methyl R⁸⁶ R⁸⁶ methyl R⁸⁶ R⁸⁶ —O— 350 methyl methyl R⁸⁶methyl methyl R⁸⁶ —O—Si(CH₃)₂—O— 351 methyl methyl R⁸⁶ methyl methyl R⁸⁶—O—Si(CH₃)(Ph)—O— 352 methyl methyl R⁸⁶ methyl methyl R⁸⁶—O—Si(CH₃)₂—O—Si(CH₃)₂—O— 353 methyl methyl R⁸⁶ methyl methyl R⁸⁶—O—Si(CH₃)₂—O—Si(CH₃)₂—O—Si(CH₃)₂—O— 354 methyl —OSiMe₃ R⁸⁶ methyl—OSiMe₃ R⁸⁶ —O— 355 methyl phenyl R⁸⁶ methyl phenyl R⁸⁶ —O— 356 i-propyli-propyl R⁸⁶ i-propyl i-propyl R⁸⁶ —O— 357 cyclopentyl cyclopentyl R⁸⁶cyclopentyl cyclopentyl R⁸⁶ —O— 358 phenyl phenyl R⁸⁶ phenyl phenyl R⁸⁶—O— 359 phenyl R⁸⁶ R⁸⁶ phenyl R⁸⁶ R⁸⁶ —O— 360 R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶ R⁸⁶—O—

In this table,

Further suitable compounds of the formula (XI) and/or (XI*) arespecified hereinafter. R therein is independently Me, phenyl or R⁸⁶,where at least one R radical is R⁸⁶:

In a very particularly preferred embodiment, the present inventionrelates to an OLED which, as well as at least one metal-carbene complexof the general formula (I), comprises at least one compound of thegeneral formula (X), in which case the compound of the formula (X) ismost preferably at least one of the compounds specified below:

In the aforementioned compounds, T is O or S, preferably O. When morethan one T occurs in the molecule, all T groups have the samedefinitions.

In addition to the compounds of the formula (X), according to thepresent invention, it is also possible to use crosslinked or polymericmaterials comprising repeat units based on the general formula (X) incrosslinked or polymerized form together with at least one heteroelepticcomplex of the general formula (I). Like the compounds of the generalformula (X), the latter are preferably used as matrix materials.

The crosslinked or polymeric materials have outstanding solubility inorganic solvents, excellent film-forming properties and relatively highglass transition temperatures. In addition, high charge carriermobilities, high stabilities of color emission and long operating timesof the corresponding components can be observed when crosslinked orpolymeric materials according to the present invention are used inorganic light-emitting diodes (OLEDs).

The crosslinked or polymerized materials are particularly suitable ascoatings or in thin films since they are thermally and mechanicallystable and relatively defect-free.

The crosslinked or polymerized materials comprising repeat units basedon the general formula (X) can be prepared by a process comprising steps(a) and (a):

-   -   (a) preparation of a crosslinkable or polymerizable compound of        the general formula (X) where at least one of the a″ R⁵⁵        radicals or at least one of the b′ R⁵⁶ radicals is a        crosslinkable or polymerizable group attached via a spacer, and    -   (b) crosslinking or polymerization of the compound of the        general formula (X) obtained from step (a).

The crosslinked or polymerized materials may be homopolymers, whichmeans that exclusively units of the general formula (X) are present incrosslinked or polymerized form. They may also be copolymers, whichmeans that further monomers are present in addition to the units of thegeneral formula (X), for example monomers with hole-conducting and/orelectron-conducting properties, in crosslinked or polymerized form.

In a further preferred embodiment of the inventive OLED, it comprises anemission layer comprising at least one inventive heteroeleptic complexof the general formula (I), at least one matrix material of the formula(X), and optionally at least one further hole-transporting matrixmaterial.

The inventive OLEDs can be used in all devices in whichelectroluminescence is useful. Suitable devices are preferably selectedfrom stationary and mobile visual display units and illumination means.The present invention therefore also relates to a device selected fromthe group consisting of stationary visual display units and mobilevisual display units and illumination means, comprising an inventiveOLED.

Stationary visual display units are, for example, visual display unitsof computers, televisions, visual display units in printers, kitchenappliances and advertising panels, illuminations and information panels.Mobile visual display units are, for example, visual display units incellphones, laptops, digital cameras, mp-3 players, smartphones,vehicles, and destination displays on buses and trains.

In addition, the inventive heteroleptic complexes of the general formula(I) can be used in OLEDs with inverse structure. The inventive complexesare preferably used in turn in these inverse OLEDs in the light-emittinglayer. The structure of inverse OLEDs and the materials typically usedtherein are known to those skilled in the art.

A further embodiment of the present invention is a white OLED comprisingat least one heteroleptic complex of the general formula (I). In apreferred embodiment, the heteroleptic complex of the general formula(I) is employed in the white OLED as emitter material. Preferredembodiments of the heteroleptic complex of the general formula (I) arementioned before. Beside the at least one heteroleptic complex of thegeneral formula (I) the white OLED may comprise at least one compound ofthe formula (X). The compound of formula (X) is preferably employed asmatrix material. Preferred compounds of the formula (X) are mentionedbefore.

In order to obtain white light, the OLED must generate light whichcolors the entire visible range of the spectrum. However, organicemitters normally emit only in a limited portion of the visiblespectrum—i. e. are colored. White light can be generated by thecombination of different emitters. Typically, red, green and blueemitters are combined. However, the prior art also discloses othermethods for formation of white OLEDs, for example the triplet harvestingapproach. Suitable structures for white OLEDs or methods for formationof white OLEDs are known to those skilled in the art.

The present invention also relates to an organic electronic component,preferably an organic light-emitting diode (OLED), organic photovoltaiccell (OPV), organic filed-effect transistor (OFET) or light-emittingelectrochemical cell (LEEC), comprising a least one inventiveheteroleptic complex of the general formula (I).

EXAMPLES

The examples which follow, especially the methods, materials,conditions, process parameters, apparatus and the like, detailed in theexamples, are intended to support the present invention, but not torestrict the scope of the present invention.

N-(2,6-Diisopropylphenyl)-2-phenylimidazole L1 is synthesizedanalogously to example 14 in WO2006/121811. The synthesis of5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole C1 is effectedaccording to D. Enders, K. Breuer, G. Raabe, J. Runsink, J. H. Teles,J.-P. Melder, K. Ebel, S. Brode, Angew. Che-m. 1995, 107, 9, 1119-1122or D. Enders, K. Breuer, U. Kallfass, T. Balensiefer, Synthesis 2003, 8,1292-1295. 3-(2,6-Dimethylphenyl)-7-methylimidazo[1,2-f]phenanthridineL3 is synthesized analogously to example 10 in WO 2007/095118. Thesynthesis of the ligand precursor1-isopropyl-1,2,4-triazolo[4,3-f]phenanthridinium iodide C3 is effectedas described in WO 2009/050281. The synthesis of the exciton and holeblocker 2,8-bis(triphenylsilyl)-dibenzofuran LB1 is disclosed insynthesis example 4g in WO 2009/003898.

All experiments are performed in protective gas atmosphere.

Example 1

μ-Dichloro Dimer D1:

3.50 g (11.5 mmol) of 1-(2,6-diisopropylphenyl)-2-phenyl-1H-imidazole L1are initially charged in 200 ml of 2-ethoxyethanol/water (ratio 3/1) andadmixed with 1.84 g (5.2 mmol) of iridium(III) chloride trihydrate. Thereaction mixture is heated at reflux for 18 h. After cooling, 50 ml ofdistilled water are added. The precipitate is filtered off, washed withdistilled water and dried. This gives 3.50 g (80%) of p-dichloro dimerD1 as a yellow powder.

¹H NMR (CD₂Cl₂, 400 MHz):

δ=0.95 (d, ³J_(H,H)=6.9 Hz, 12H), 1.18 (d, ³J_(H,H)=6.9 Hz, 12H), 1.27(d, ³J_(H,H)=6.9 Hz, 12H), 1.34 (d, ³J_(H,H)=6.9 Hz, 12H), 2.80-2.91 (m,8H), 6.08 (d, ³J_(H,H)=7.7 Hz, 4H), 6.24 (d, ³J_(H,H)=7.7 Hz, 4H), 6.39(pt, ³J_(H,H)=7.5 Hz, 4H), 6.53 (pt, ³J_(H,H)=7.5 Hz, 4H),6.97 (d,J_(H,H)=1.5 Hz, 4H), 7.39-7.45 (m, 8H), 7.59 (t, ³J_(H,H)=7.8 Hz, 4H),7.67 (d, J_(H,H)=1.5 Hz, 4H).

Complex Em1-s:

2.37 g (7.2 mmol) of5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole C1 are heated to90° C. under reduced pressure for 18 h. After cooling to roomtemperature, first 100 ml of anhydrous toluene and then a suspension of3.00 g (1.8 mmol) of chloro dimer D1 and 150 ml of anhydrous toluene areadded. The mixture is heated to 90° C. for 2 h. The white precipitateformed (1.15 g, imidazolium chloride C1*) is filtered off. The filtrateis washed with 3×40 ml of saturated NaHCO₃ solution and 1×40 ml ofdistilled water, dried over MgSO₄ and freed of the solvent under reducedpressure. The residue is washed with 2×50 ml of methanol, recrystallizedfrom methylene chloride/methanol and then recrystallized fromnitromethane. This gives 3.2 g of the complex Em1-s as a yellow powder(82%).

Em1-s: The configuration of Em1-s corresponds to the configuration ofthe pseudo-meridional isomer S1a or S1b. Em1-s is present as theracemate; for crystal structure see FIG. 1 , only one enantiomer isdepicted, large sphere=C, small sphere=H. Sample for the x-ray structureanalysis is crystallized from nitromethane (nitromethane still presentin the crystals).

¹H NMR (CD₂Cl₂, 400 MHz):

δ=0.88 (d, ³J_(H,H)=6.8 Hz, 3H), 0.91 (d, ³J_(H,H)=6.9 Hz, 9H), 1.14 (d,³J_(H,H)=6.9 Hz, 3H), 1.16 (d, ³J_(H,H)=6.8 Hz, 3H), 1.20 (d,³J_(H,H)=6.9 Hz, 3H), 1.28 (d, ³J_(H,H)=6.9 Hz, 3H), 2.08 (sept,³J_(H,H)=6.7 Hz, 1H), 2.65-2.77 (m, 3H), 6.08-6.15 (m, 3H), 6.19-6.25(m, 2H), 6.42-6.45 (m, 1H), 6.50-6.52 (m, 2H), 6.67 (s, b, 2H), 6.71(dt, ³J_(H,H)=7.4 Hz, J=1.2 Hz, 1H), 6.75 (d, J=1.5 Hz, 1H), 6.79-6.87(m, 6H), 7.00-7.07 (m, 2H), 7.28-7.43 (m, 9H), 7.50 (t, ³J_(H,H)=7.8 Hz,1H), 7.56 (t, ³J_(H,H)=7.8 Hz, 1H), 7.71 (d, ³J_(H,H)=7.5 Hz, 1H).

Photoluminescence (in a film, 2% in PMMA):

λ=460, 490 nm, CIE: (0.19; 0.34)

Example 2

Complex Em1-i:

-   -   racemic in each case, only one enantiomer of each depicted

A solution of 1.6 g of complex Em1-s in 200 ml of 3-methoxypropionitrileis irradiated at room temperature with a blacklight blue lamp for 5 h(Osram, L18W/73, λ_(max)=370-380 nm). The solvent is removed underreduced pressure. The residue is washed with methanol and recrystallizedfrom methylene chloride/methanol. This gives 1.2 g of Em1-i as a lemonyellow powder (75%).

The configuration of Em1-i corresponds to the configuration IVa or IVbof the pseudo-facial isomer S4a or S4b. Emi-i is present as theracemate; for crystal structure see FIG. 2 , the sample for the x-raystructure analysis is crystallized from cyclohexane/ethyl acetate(cyclohexane still present in the crystals).

¹H NMR (CD₂Cl₂, 500 MHz):

δ=0.46 (d, ³J_(H,H)=6.8 Hz, 3H), 0.75 (d, ³J_(H,H)=6.8 Hz, 3H), 0.81 (d,³J_(H,H)=6.8 Hz, 3H), 1.01 (d, ³J_(H,H)=6.8 Hz, 3H), 1.09 (d,³J_(H,H)=6.9 Hz, 3H), 1.14 (d, ³J_(H,H)=6.9 Hz, 3H), 1.17 (d,³J_(H,H)=6.9 Hz, 3H), 1.26 (d, ³J_(H,H)=6.8 Hz, 3H), 1.50 (sept,³J_(H,H)=6.8 Hz, 1H), 2.49-2.60 (m, 3H), 6.01 (d, J=1.3 Hz, 1H), 6.10(t, ³J_(H,H)=8.2 Hz, 2H), 6.34 (d, J=1.4 Hz, 1H), 6.38 (d, ³J_(H,H)=7.2Hz, 1H), 6.41-6.45 (m, 2H), 6.57-6.73 (m, 5H), 6.85 (d, J=1.4 Hz, 1H),6.96-7.00 (m, 1H), 7.11 (d, J=1.4 Hz, 1H), 7.17-7.42 (m, 14H), 7.46 (t,³J_(H,H)=7.8 Hz, 1H), 7.54 (t, ³J_(H,H)=7.8 Hz, 1H), 7.68 (d,J_(H,H)=8.2 Hz, 1H).

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=456, 488 nm, CIE: (0.21;0.37)

The photoluminescence quantum yield of the facial isomer Em1-i is 1.36times the quantum yield of the meridional isomer Em1-s.

Example 3

4-Bromodibenzofuran

100.00 g (99%, 588.6 mmol) of dibenzofuran are dissolved in 800 ml ofanhydrous THF and admixed at −40° C. with 400 ml (640.0 mmol) of n-BuLi(1.6M in hexane). The cooling bath is removed. The reaction solution isallowed to come to room temperature in a water bath within approx. 30min and stirred for a further two hours. Thereafter, it is cooled to−78° C. and a solution of 160.34 g (99%, 844.9 mmol, 73.55 ml) of1,2-dibromoethane in 80 ml of anhydrous THF is added dropwise. Thecooling bath is removed, and the mixture is allowed to come to roomtemperature in a water bath within approx. 30 min and stirred for afurther two hours. Subsequently, 60 ml of saturated sodium chloridesolution are added cautiously (slightly exothermic reaction, temperaturerise 1-2° C.). The organic phase is removed and freed of the solventunder reduced pressure. The oily red-brown residue is taken up in 900 mlof dichloromethane and washed successively with 500 ml of HCl solution(1N) and 400 ml of water. The organic phase is dried over magnesiumsulfate and freed of the solvent under reduced pressure. In the courseof cooling, a yellowish solid precipitates out, which is comminuted in amortar and washed on a frit with 2×150 ml of isopropanol. After drying,120.36 g of beige powder are obtained (according to GC and NMR:DBF/Br-DBF ratio=10/90, corresponds to 111.93 g of Br-DBF/76% yield).After removing the solvent, a further 15.84 g of a mixture ofdibenzofuran and 4-bromodibenzofuran (comprises a further approx. 7.8g/5% Br-DBF) are obtained from the isopropanol solution. This mixturecan likewise be used in the further stages.

¹H NMR (CDCl₃, 500 MHz):

δ=7.92 (d, ³J_(H,H)=7.8 Hz, 1H), 7.86 (dd, ³J_(H,H)=7.7 Hz, ⁴J_(H,H)=1.0Hz, 1H), 7.65 (d, ³J_(H,H)=8.2 Hz, 1H), 7.61 (dd, ³J_(H,H)=7.8 Hz,⁴J_(H,H)=1.1 Hz, 1H), 7.50 (dt, ³J_(H,H)=8.2 Hz, J_(H,H)=1.3 Hz, 1H),7.37 (dt, ³J_(H,H)=7.8 Hz, J_(H,H)=0.8 Hz, 1H), 7.21 (t, ³J_(H,H)=7.8Hz, 1H).

1-Dibenzofuran-4-yl-1H-imidazole

119.00 g of the first stage (comprise 110.66 g, 447.9 mmol of4-bromodibenzofuran) are dissolved in 700 ml of dimethylformamide andadmixed successively with 37.15 g (545.7 mmol) of imidazole, 15.80 g(83.0 mmol) of copper(I) iodide and 83.20 g (602.0 mmol) of potassiumcarbonate. The mixture is stirred at 150° C. for 48 h, in the course ofwhich a further 3.75 g (55.1 mmol) of imidazole are added after 24 h anda further 1.93 g (28.3 mmol) after 44 h. Thereafter, the mixture iscooled to room temperature and the insoluble constituents are filteredoff. The filtrate is concentrated to dryness. The residue is taken up in500 ml of methylene chloride, washed successively with 150 ml of ammoniasolution (25%) and 150 ml of water, dried over magnesium sulfate andconcentrated. This gives 82.23 g of crude product, which is used in thenext stage without further purification (78% crude yield).

3-Dibenzofuran-4-yl-1-methyl-3H-imidazol-1-ium Iodide C2

82.03 g (350.1 mmol) of 1-dibenzofuran-4-yl-1H-imidazole (crude product)are dissolved in 1 l of tetrahydrofuran and admixed slowly with 246.06 g(1.733 mol) of methyl iodide. The mixture is stirred at room temperaturefor 65 h. The precipitate formed is filtered off, washed with 1 l oftetrahydrofuran and dried. This gives 98.41 g (261.6 mmol, 75%) of beigepowder.

¹H NMR (DMSO, 500 MHz):

δ=10.00 (s, 1H, NCHN), 8.49 (t, J=1.9 Hz, 1H, CH_(Aryl)), 8.41 (dd,³J_(H,H)=7.8 Hz, J=1.0 Hz, 1H, CH_(Aryl)). 8.32-8.30 (m, 1H, CH_(Aryl)),8.15 (t, J=1.8 Hz, 1H, CH_(Aryl)), 7.96 (dd, ³J_(H,H)=7.9 Hz, J=1.0 Hz,1H, CH_(Aryl)), 7.84 (d, ³J_(H,H)=8.4 Hz, 1H, CH_(Aryl)), 7.69-7.65 (m,2H, CH_(Aryl)), 7.53 (dt, ³J_(H,H)=7.5 Hz, J=0.9 Hz, 1H, CH_(Aryl)),4.12 (s, 3H, CH₃).

Complex Em2-s:

1.01 g (2.7 mmol) of imidazolium iodide C2 and 0.31 g (1.3 mmol) of Ag₂Oare stirred in 200 ml of anhydrous acetonitrile at room temperature for18 h. Then the solvent is removed under reduced pressure. The residue istaken up in 300 ml of anhydrous THF and 1.50 g (0.9 mmol) of chlorodimer D1 are added. Thereafter, the mixture is heated at reflux for 24h. After cooling, the reaction solution is filtered. The filtrate isfreed of the solvent under reduced pressure. The residue is washed withmethanol and, after drying, 1.2 g of the complex Em2-s are obtained as ayellow powder (64%).

¹H NMR (CD₂Cl₂, 500 MHz):

δ=0.86 (d, ³J_(H,H)=6.9 Hz, 3H), 0.96 (d, ³J_(H,H)=6.8 Hz, 3H), 1.00 (d,³J_(H,H)=6.7 Hz, 3H), 1.02 (d, ³J_(H,H)=7.1 Hz, 3H), 1.03 (d,³J_(H,H)=7.1 Hz, 3H), 1.06 (d, ³J_(H,H)=6.9 Hz, 3H), 1.21 (d,³J_(H,H)=7.0 Hz, 3H), 1.23 (d, ³J_(H,H)=7.0 Hz, 3H), 2.15 (sept,³J_(H,H)=6.9 Hz, 1H), 2.39 (sept, ³J_(H,H)=6.9 Hz, 1H), 2.77-2.85 (m,2H), 3.34 (s, 3H), 6.17 (bd, ³J_(H,H)=7.8 Hz, 1H), 6.20 (bd,³J_(H,H)=7.8 Hz, 1H), 6.41 (d, J=1.5 Hz, 1H), 6.44-6.52 (m, 2H), 6.54(d, J=1.5 Hz, 1H), 6.67-6.79 (m, 5H), 6.89 (d, ³J_(H,H)=7.4 Hz, 1H),6.95 (d, J=1.9 Hz, 1H), 7.16 (bd, ³J_(H,H)=7.3 Hz, 1H), 7.29-7.41 (m,7H), 7.51-7.55 (m, 2H), 7.61 (bd, ³J_(H,H)=8.1 Hz, 1H), 7.89 (bd,³J_(H,H)=8.3 Hz, 1H), 8.46 (d, J=1.9 Hz, 1H).

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=460, 491 nm, CIE: (0.18;0.33)

Example 4

Complex Em2-i:

A solution of 0.90 g of complex Em2-s in 200 ml of3-methoxypropionitrile is irradiated at room temperature with ablacklight blue lamp for 3 h (Osram, L18W/73, λ_(max)=370-380 nm). Thesolvent is removed under reduced pressure. The residue is carefullywashed with methanol. This gives 0.63 g Em2-i as a yellow powder (70%).

The configuration of Em2-i corresponds to the configuration IVa or IVbof the pseudo-facial isomer S4a or S4b. Em2-1 is present as theracemate; for crystal structure see FIG. 3 , the sample for the x-raystructure analysis was crystallized from tetrahydrofuran/n-heptane.

¹H NMR (CD₂Cl₂, 400 MHz):

δ=0.72 (d, ³J_(H,H)=6.8 Hz, 3H), 0.85 (d, ³J_(H,H)=6.8 Hz, 3H), 0.90 (d,³J_(H,H)=6.8 Hz, 3H), 0.99 (d, ³J_(H,H)=6.9 Hz, 3H), 1.02 (d,³J_(H,H)=6.8 Hz, 3H), 1.11 (d, ³J_(H,H)=6.9 Hz, 3H), 1.19 (d,³J_(H,H)=7.1 Hz, 3H), 1.21 (d, ³J_(H,H)=7.1 Hz, 3H), 1.90 (sept,³J_(H,H)=6.8 Hz, 1H), 2.46 (sept, ³J_(H,H)=6.8 Hz, 1H), 2.60 (sept,³J_(H,H)=6.9 Hz, 1H), 2.77 (sept, ³J_(H,H)=6.9 Hz, 1H), 3.53 (s, 3H),6.16 (bd, ³J_(H,H)=7.7 Hz, 2H), 6.38-6.56 (m, 5H), 6.65-6.69 (m, 2H),6.76-6.84 (m, 4H), 6.99 (d, J=1.9 Hz, 1H), 7.22 (d, ³J_(H,H)=7.7 Hz,1H), 7.27-7.37 (m, 6H), 7.49-7.60 (m, 3H), 7.86 (bd, ³J_(H,H)=7.2 Hz,1H), 8.38 (d, J=1.9 Hz, 1H).

Photoluminescence (in a film, 2% in PMMA):

λ_(max)==462, 490 nm, CIE: (0.17; 0.29)

The photoluminescence quantum yield of the facial isomer Em2-i is 1.44times the quantum yield of the isomer Em2-s.

Example 5

Complex Em3-s:

6.0 g (15.5 mmol) of 1-isopropyl-1,2,4-triazolo[4,3-f]phenanthridiniumiodide C3 and 2.9 g (12.3 mmol) of Ag₂O are stirred in 400 ml of dioxaneat room temperature for 40 h. Subsequently, 2.6 g (1.6 mmol) of chlorodimer D1 are added and the mixture is heated to reflux for 24 h. Aftercooling to room temperature, the precipitate is filtered off and washedwith dichloromethane. The combined filtrates are concentrated to drynessand purified by column chromatography (silica gel, dichloromethane).After drying, 2.1 g of Em3-s are obtained as yellow powder (64%).

¹H NMR (CD₂Cl₂, 500 MHz):

δ=0.79 (d, 3H), 0.89 (d, 3H), 0.90 (d, 3H), 0.97 (d, 6H), 1.02 (d, 3H),1.10 (d, 3H), 1.15 (d, 3H), 1.16 (d, 3H), 1.47 (d, 3H), 2.03 (sept, 1H),2.47 (sept, 1H), 2.65 (sept, 1H), 2.76 (sept, 1H), 4.47 (sept, 1H), 6.13(d, 1H), 6.21 (d, 1H), 6.35 (d, 1H), 6.46 (me, 3H), 6.58 (dd, 2H),6.65-6.76 (m, 3H), 6.93 (dd, 1H), 7.09 (dd, 1H), 7.15 (d, 1H), 7.25 (dd,1H), 7.28-7.33 (m, 3H), 7.44-7.52 (m, 2H), 7.58 (dd, 1H), 7.67-7.76 (m,2H), 8.39 (dd, 1H), 8.43 (d, 1H).

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=457, 489 nm, CIE: (0.18; 0.32)

Example 6

Complex Em3-i:

A suspension of 2.1 g of Em3-s in 2000 ml of acetonitrile is irradiatedwith a moderate-pressure mercury immersion lamp at room temperature for8 h (TQ150 with Duran sheath). Subsequently, the solvent is removedunder reduced pressure. The residue was stirred twice with acetone andfiltered. 1.6 g of Em3-i were obtained as a yellow powder (76%).

¹H NMR (CD₂Cl₂, 500 MHz):

δ=0.68 (d, 3H), 0.75 (d, 3H), 0.82 (d, 3H), 0.96 (d, 3H), 0.99 (d, 3H),1.05 (d, 3H), 1.13 (d, 3H), 1.20 (d, 3H), 1.24 (d, 3H), 1.60 (d, 3H),1.79 (sept, 1H), 2.42 (sept, 1H), 2.51 (sept, 1H), 2.76 (sept, 1H), 4.56(sept, 1H), 6.10 (dd, 2H), 6.30-6.35 (m, 1H), 6.38-6.45 (m, 2H), 6.53(d, 1H), 6.61 (dd, 1H), 6.68 (d, 1H), 6.73 (d, 1H), 6.74-6.78 (m, 2H),6.79 (d, 1H), 6.96 (dd, 1H), 7.07-7.15 (m, 1H), 7.19 (d, 1H), 7.22 (d,1H), 7.27-7.34 (m, 3H), 7.47 (dd, 1H), 7.49 (dd, 1H), 7.66-7.72 (m, 2H),8.34 (d, 1H), 8.40 (d, 1H).

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=456, 487 nm, CIE: (0.19; 0.32)

The photoluminescence quantum yield of the isomer Em3-i is 1.21 timesthe quantum yield of the isomer Em3-s.

Example 7 4-Methyl-1.3-diphenyl-1H-[1,2,4]-triazolium Iodide C4

Stage 1: Benzonitrile (51.5 g, 0.50 mol) is admixed with ethanol(anhydrous, 25 ml). Then a constant stream of HCl gas is introduced over2 h and the mixture is subsequently stirred at room temp. for 48 h, inthe course of which a solid forms. The solvent is drawn off from thereaction mixture under reduced pressure (95 g).

Stages 2+3: 12 g of stage 1 (64.6 mmol) are again dissolved in EtOH (120ml), and phenylhydrazine (9.4 g, 84 mmol, 1.3 equiv.) is added, in thecourse of which a solid forms. Triethylamine (22 ml, 162 mmol, 2.5equiv.) is added and then the mixture is stirred at room temp. for 16 h.The solvent is again removed from the reaction mixture under reducedpressure at room temp., such that the amidrazone formed remains, stillmoist. After the addition of formic acid (200 ml), the mixture is heatedto reflux for 3.5 h. After a further 48 h at room temp., the mixture iscautiously added to an aq. potassium carbonate solution (44%, 900 ml),cooled to 0° C. After the addition of CH₂Cl₂ (500 ml), the phases areseparated, and the organic phase is dried over Na₂SO₄ and concentratedunder reduced pressure. The sample is recrystallized fromdichloromethane/petroleum ether, from which slightly contaminatedproduct is obtained (5.5 g, 40%). The mother liquor is column-filtered(CH₂Cl₂/n-hexane), from which a further batch of clean product isobtained (1.7 g, 12%).

Stage 4: The triazole of the preceding stage (1.5 g, 66 mmol) isdissolved in THF (anhydrous, 40 ml), admixed with Mel (14 ml) and heatedto reflux for 5 days. The solid obtained is filtered off, recrystallizedrepeatedly (CH₂Cl₂/n-hexane) and dried (780 mg, 32%).

¹H NMR (400 MHz, CD₂Cl₂):

δ=4.26 (s, 3H), 7.53-7.71 (m, 6H), 7.74-7.76 (m, 2H), 8.09-8.11 (m, 2H),12.27 (s, 1H).

Complex Em4-s:

0.40 g (1.1 mmol) of imidazolium iodide C4 and 0.13 g (0.56 mmol) ofAg₂O are stirred in 50 ml of anhydrous acetonitrile at room temperaturefor 18 h. Then a solution of 0.61 g (0.37 mmol) of chloro dimer D1 in 25ml of anhydrous acetonitrile is added. Thereafter, the mixture is heatedto reflux for 6 h and then stirred at room temperature for another 16 h.After cooling, the reaction solution is filtered. The filtrate is freedof the solvent under reduced pressure. After washing the residue withmethanol, 0.2 g of the complex Em4-s is obtained as a yellow powder(26%).

¹H NMR (500 MHz, CD₂Cl₂):

δ=0.91 (d, ³J_(H,H)=6.9 Hz, 3H), 0.95 (d, ³J_(H,H)=7.1 Hz, 3H), 0.97 (d,³J_(H,H)=7.1 Hz, 3H), 0.98 (d, ³J_(H,H)=6.8 Hz, 3H), 1.00 (d,³J_(H,H)=6.9 Hz, 3H), 1.05 (d, ³J_(H,H)=6.9 Hz, 3H), 1.20 (d,³J_(H,H)=6.9 Hz, 3H), 1.21 (d, ³J_(H,H)=6.9 Hz, 3H), 2.17 (sept,³J_(H,H)=6.8 Hz, 1H), 2.40 (sept, ³J_(H,H)=6.9 Hz, 1H), 2.75-2.82 (m,2H), 3.36 (s, 3H), 6.17 (bt, ³J_(H,H)=7.0 Hz, 2H), 6.43-6.50 (m, 3H),6.62 (d, J=1.5 Hz, 1H), 6.66-6.82 (m, 6H), 6.88 (dd, ³J_(H,H)=7.1 Hz,J=1.3 Hz, 1H), 6.96 (dt, ³J_(H,H)=7.4 Hz, J=1.5 Hz, 1H), 7.08 (bd,³J_(H,H)=6.7 Hz, 1H), 7.31-7.37 (m, 4H), 7.51-7.59 (m, 6H), 7.69-7.72(m, 2H).

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=458, 488 nm, CIE: (0.19; 0.33)

Example 8

Complex Em4-i:

A solution of 0.15 g of complex Em4-s in 200 ml of3-methoxypropionitrile is irradiated with a blacklight blue lamp at roomtemperature for 2 h (Osram, L18W/73, λ_(max)=370-380 nm). The solvent isremoved under reduced pressure. The residue is carefully washed withmethanol. This gives 0.05 g Em4-i as a yellow powder (33%).

¹H NMR (500 MHz, CD₂Cl₂):

δ=0.71 (d, ³J_(H,H)=6.9 Hz, 3H), 0.84 (d, ³J_(H,H)=6.8 Hz, 3H), 0.88 (d,³J_(H,H)=6.9 Hz, 3H), 1.03 (d, ³J_(H,H)=6.8 Hz, 3H), 1.06 (d,³J_(H,H)=6.7 Hz, 3H), 1.07 (d, ³J_(H,H)=6.8 Hz, 3H), 1.18 (d,³J_(H,H)=6.9 Hz, 3H), 1.19 (d, ³J_(H,H)=6.9 Hz, 3H), 1.89 (sept,³J_(H,H)=6.8 Hz, 1H), 2.50 (sept, ³J_(H,H)=6.9 Hz, 1H), 2.58 (sept,³J_(H,H)=6.9 Hz, 1H), 2.73 (sept, ³J_(H,H)=6.9 Hz, 1H), 6.17 (bd,³J_(H,H)=7.8 Hz, 2H), 6.42-6.52 (m, 3H), 6.60 (dt, ³J_(H,H)=7.6 Hz,J=1.3 Hz, 1H), 6.64-6.70 (m, 4H), 6.76-6.78 (m, 2H), 6.81 (d, J=61.4 Hz,1H), 6.91-6.94 (m, 2H), 7.27-7.38 (m, 4H), 7.50-7.56 (m, 6H), 7.75-7.77(m, 2H).

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=456, 488 nm, CIE: (0.19; 0.33)

The photoluminescence quantum yield of the isomer Em4-i has 1.40 timesthe quantum yield of the isomer Em4-s.

Example 9 3,4-Diphenyl-1-o-tolyl-4H-[1,2,4]-triazolium Iodide C5

Stage 1: Aq. NaHCO₃ solution (5%, 330 g, 190 mmol, 2.0 equiv.) is addedat room temp. to a suspension of o-tolylhydrazine hydrochloride (15 g,97 mmol) in methyl chloride (450 ml). After stirring for 30 minutes, thebiphasic solution is phase-separated. The organic phase is dried overNa₂SO₄, freed of the solvent and dried under reduced pressure at 60° C.to isolate tolylhydrazine as a pale yellow solid (7.3 g, 62%).

Stage 2: Benzoyl chloride (8.4 g, 60 mmol, 1.0 equiv.) is initiallycharged in toluene (anhydrous, 60 ml) and cooled to 5° C. Then aniline(5.6 g, 60 mmol, 1.0 equiv.) is added, and the reaction mixture isheated to reflux for 16 h and then stirred at room temp. for a further48 h. Then the mixture is heated to 80° C., thionyl chloride (21.4 g,180 mmol, 3.0 equiv.) is added at this temperature and the mixture isstirred for a further 2 h. Then the mixture is cooled to room temp. andthe excess thionyl chloride is drawn off under reduced pressure. Thereaction mixture is admixed with THF (anhydrous, 180 ml) andtriethylamine (9.1 g, 90 mmol, 1.5 equiv.) and cooled to 5° C., and thenthe tolylhydrazine of stage 1 (7.3 g, 60 mmol), dissolved in THF (20ml), is added. The mixture is stirred at room temperature for 16 h.After the removal of the solvent, the residue is recrystallized fromacetic acid (2%, 150 ml), washed with iPrOH (80 ml, 20 ml) and dried(10.3 g, 57%).

Stage 3: Triethyl orthoformate (9.0 ml, 8.1 g, 56 mmol, 5.6 equiv.) and3 g of the hydrazone of stage 2 (10 mmol) are initially charged,ammonium iodide (1.4 g, 10 mmol, 1.0 equiv.) is added and the suspensionis heated to reflux for 7 h. After cooling, the solid is filtered offwith suction and washed repeatedly with n-hexane and ethyl acetate, fromwhich the iodide salt is obtained as a gray powder (3.2 g, 73%).

¹H NMR (400 MHz, DMSO):

δ=2.55 (s, 3H), 7.47-7.90 (m, 14H), 11.07 (s, 1H).

Complex Mixture Em5-s:

1.12 g (2.5 mmol) of imidazolium iodide C5 are suspended in 100 ml ofanhydrous toluene. At 0° C., 8.2 ml (4.1 mmol) of potassiumbis(trimethylsilyl)amide (0.5M in toluene) are added dropwise within 5min. The solution formed is allowed to warm up to 10° C. and admixedwith a suspension of 1.42 g (0.85 mmol) of chloro dimer D1 and 75 ml ofanhydrous toluene. The reaction mixture is heated to 90° C. and stirredat this temperature for 2 h. After cooling, the precipitate is removed.The filtrate is washed successively with 3×30 ml of aqueous NaHCO₃solution and 1×30 ml of water, dried over MgSO₄ and freed of the solventunder reduced pressure. The residue is purified by column chromatography(solvent: cyclohexane/acetone=4/1). This gives 1.2 g (63%) Em5-s as amixture of two cyclometalation isomers.

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=461, 489 nm, CIE: (0.19; 0.33)

Example 10

Complex Mixture Em5-i:

A solution of 0.60 g of Em5-s complex mixture in 200 ml of3-methoxypropionitril is irradiated with a blacklight blue lamp at roomtemperature for 7 h (Osram, L18W/73, λ_(max)=370-380 nm). The solvent isremoved under reduced pressure. The residue is carefully washed withmethanol. This gives 0.10 g of Em5-i as a pale yellow powder (17%, againmixture of two cyclometalation isomers).

MS (Maldi):

m/e=1110 (M+H)⁺

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=456,487 nm, CIE: (0.20; 0.34)

The photoluminescence quantum yield of the isomerized Em5-i complexmixture has 1.50 times the quantum yield of the Em5-s complex mixture.

Example 11 1-Methyl-2-phenyl-1 H-imidazole L-2

13.0 g (90 mmol) of 2-phenylimidazole are dissolved in 600 ml of DMF,admixed slowly with 4.0 g (100 mmol) of sodium hydride (60% in mineraloil) and stirred at room temperature for 30 min. Then 14.0 g (99 mmol)of methyl iodide are added. The reaction mixture is stirred at roomtemperature for 1.5 h and then admixed cautiously with 350 ml of water.The mixture is extracted with 2×200 ml of ethyl acetate. The extract isdried over sodium sulfate and concentrated. This gives 12.0 g (84%) L2.

¹H NMR (400 MHz, CD₂Cl₂):

δ=3.74 (s, 3H), 7.00 (s, 1H), 7.05 (s, 1H), 7.40-7.43 (m, 1H), 7.45-7.48(m, 2H), 7.62-7.63 (m, 2H).

μ-Dichloro Dimer D2:

The synthesis is performed analogously to D1. The precipitate obtainedis extracted with dichloromethane. After removing the solvent, D2 isobtained from the extract in a yield of 36%.

¹H NMR (CD₂Cl₂, 400 MHz):

δ=4.13 (s, 12H), 6.05 (d, ³J_(H,H)=7.7 Hz, 4H), 6.55 (t, ³J_(H,H)=7.5Hz, 4H), 6.74 (t, ³J_(H,H)=7.5 Hz, 4H), 6.94 (s, 4H), 7.27 (s, 4H), 7.37(d, ³J_(H,H)=7.7 Hz, 4H).

Complex Em6-s:

1.20 g (3.6 mmol) of5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole C1 are heated to90° C. under reduced pressure for 20 h. After cooling to roomtemperature, first 1.2 l of anhydrous toluene and then 0.99 g (0.9 mmol)of chloro dimer D2 are added. The mixture is heated to reflux for 8 h.The precipitate formed is filtered off. The filtrate is concentrated toapprox. 800 ml and washed successively with 3×500 ml of saturated NaHCO₃solution and 1×500 ml of distilled water, dried over Na₂SO₄ and freed ofthe solvent under reduced pressure. The residue is purified by columnchromatography (cyclohexane/acetone=5/1). This gives 118 mg of thecomplex Em6-s (8%).

¹H NMR (CD₂Cl₂, 400 MHz):

δ=3.95 (s, 3H), 4.03 (s, 3H), 6.00 (bd, ³J_(H,H)=7.3 Hz, 1H), 6.23 (bt,³J_(H,H)=7.3 Hz, 1H), 6.27 (d, J=1.5 Hz, 1H), 6.47 (bd, ³J_(H,H)=7.1 Hz,1H), 6.51 (d, J=1.5 Hz, 1H), 6.60 (bt, ³J_(H,H)=7.5 Hz, 1H), 6.67-6.72(m, 4H), 6.79-6.88 (m, 6H), 6.95 (dt, ³J_(H,H)=7.5 Hz, J=1.5 Hz, 1H),7.05 (bt, ³J_(H,H)=7.5 Hz, 1H), 7.24-7.27 (m, 2H), 7.33-7.36 (m, 4H),7.47 (bd, ³J_(H,H)=6.8 Hz, 1H), 7.61 (bd, ³J_(H,H)=6.9 Hz, 1H).

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=456, 486 nm, CIE: (0.21; 0.33)

Example 12

Complex Em7-s:

0.67 g (2.0 mmol) of5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole C1 are heated to90° C. under reduced pressure for 20 h. After cooling to roomtemperature, the residue is dissolved in 50 ml of anhydrous toluene andadded to a suspension of 1.00 g (0.9 mmol) of chloro dimer D2 and 0.36 g(1.9 mmol) of AgBF₄ in 1.2 l of anhydrous toluene. The mixture isstirred under reflux for 8 h. The precipitate formed is filtered off.The filtrate is concentrated to approx. 800 ml and washed successivelywith 3×500 ml of saturated NaHCO₃ solution and 1×500 ml of distilledwater, dried over Na₂SO₄ and freed of the solvent under reducedpressure. The residue is purified by column chromatography(cyclohexane/acetone=5/1). This gives 70 mg of the complex Em7-s (5%).

MS (Maldi):

m/e=943 (M+H)⁺

¹H NMR (CD₂Cl₂, 400 MHz):

δ=3.70 (s, 3H), 5.86 (d, J=1.3 Hz, 1H), 5.96 (bd, ³J_(H,H)=8.1 Hz, 2H),6.10 (d, J=1.3 Hz, 1H), 6.56 (bd, ³J_(H,H)=7.2 Hz, 1H), 6.72-6.75 (m,4H), 6.80 (bt, ³J_(H,H)=7.3 Hz, 1H), 6.86-6.92 (m, 3H), 6.94 (bt,³J_(H,H)=7.5 Hz, 1H), 7.02-7.12 (m, 5H), 7.19-7.40 (m, 13H), 7.56 (bd,³J_(H,H)=7.7 Hz, 1H), 7.70 (bd, ³J_(H,H)=7.0 Hz, 1H).

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=476, 502 nm, CIE: (0.22; 0.37)

Example 13

Complex Em7-s*:

0.90 g (2.7 mmol) of5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole C1 are heated to90° C. under reduced pressure for 20 h. After cooling to roomtemperature, first 800 ml of anhydrous toluene and then 0.99 g (0.9mmol) of chloro dimer D2 are added. The mixture is stirred under refluxfor 3 h. The precipitate formed is filtered off. The filtrate is washedsuccessively with 3×50 ml of saturated NaHCO₃ solution and 1×50 ml ofdistilled water, dried over MgSO₄ and freed of the solvent under reducedpressure. The residue is purified by column chromatography(cyclohexane/acetone=2/1). As well as 50 mg of the complex Em6-s, 150 mgof the complex Em7-s* are obtained.

¹H NMR (CD₂Cl₂, 500 MHz):

δ=3.86 (s, 3H), 5.95 (bd, ³J_(H,H)=7.3 Hz, 2H), 6.23 (bd, J=1.4 Hz, 1H),6.38 (bt, ³J_(H,H)=7.3 Hz, 1H), 6.44 (bd, ³J_(H,H)=7.3 Hz, 1H), 6.54(bt, ³J_(H,H)=7.5 Hz, 1H), 6.61-6.67 (m, 4H), 6.78-6.91 (m, 5H), 6.96(bt, ³J_(H,H)=7.5 Hz, 1H), 7.07-7.13 (m, 4H), 7.19-7.36 (m, 12H), 7.53(bd, ³J_(H,H)=7.0 Hz, 1H), 7.76 (bd, ³J_(H,H)=7.3 Hz, 1H).

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=482, 508 nm, CIE: (0.24; 0.40)

Example 14

μ-Dichloro Dimer D3

The synthesis is performed analogously to D1. Yield: 87%.

¹H NMR (CD₂Cl₂, 400 MHz):

δ=2.21 (s, 12H), 2.28 (s, 12H), 2.44 (s, 12H), 6.38 (d, ³J_(H,H)=7.4 Hz,4H), 7.09 (d, ³J_(H,H)=8.7 Hz, 4H), 7.19 (m, 4H), 7.30 (bd, ³J_(H,H)=8.7Hz, 4H), 7.42 (m, 8H), 7.55 (m, 4H), 7.86 (s, 4H), 8.00 (d, ³J_(H,H)=8.4Hz, 4H), 8.48 (bs, 4H).

Complex Em8-s:

0.37 g (1.1 mmol) of5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole C1 are heated to90° C. under reduced pressure for 18 h. After cooling to roomtemperature, first 120 ml of anhydrous toluene and then 0.50 g (0.28mmol) of chloro dimer D3 are added. The mixture is heated to 75° C. for3 h. The white precipitate formed is filtered off. The filtrate iswashed with 3×30 ml of saturated NaHCO₃ solution and 1×30 ml ofdistilled water, dried over MgSO₄ and freed of the solvent under reducedpressure. The residue is purified by column chromatography (silica gel,ethyl acetate:cyclohexane=1:5). This gives 0.19 g of the complex Em8-s(28%).

¹H NMR (CD₂Cl₂, 500 MHz):

δ=2.03 (s, 3H), 2.10 (s, 3H), 2.20 (s, 3H), 2.28 (s, 3H), 2.44 (s, 3H),2.48 (s, 3H), 6.21 (d, ³J_(H,H)=7.6 Hz, 1H), 6.63-7.39 (m, 28H), 7.45(d, ³J_(H,H)=7.9 Hz, 1H), 7.67 (d, ³J_(H,H)=7.9 Hz, 1H), 7.70 (d,³J_(H,H)=7.6 Hz, 1H), 8.21 (bs, 2H).

Photoluminescence (in a film, 2% in PMMA):

λ_(max)=456 nm, CIE: (0.24; 0.29)

Example 15 (Comparative Example, Noninventive)

Complex CEm1:

CEm1 corresponds to compound (N-3) from WO 2006067074

The synthesis is analogous to WO 2006067074.

λ_(PL) (PMMA): 472 nm, 491 nm, quantum yield_(PL): 2%

Owing to its very low phosphorescence quantum yield, complex CEm1 is notsuitable as an emitter in OLEDs.

Example 16 (Comparative Example, Noninventive)

Complex CEm2:

CEm2 corresponds to the compound “Compound 3” from WO 2006121811. Thesynthesis was analogous WO 2006121811.

Example 17

Production of an OLED—Comparison of Different Emitters

The ITO substrate used as the anode is cleaned first with commercialdetergents for LCD production (Deconex® 20NS, and 25ORGAN-ACID®neutralizing agent) and then in an acetone/isopropanol mixture in anultrasound bath. To eliminate possible organic residues, the substrateis exposed to a continuous ozone flow in an ozone oven for a further 25minutes. This treatment also improves the hole injection properties ofthe ITO. Next, the hole injection layer AJ20-1000 from Plexcorerespectively PEDT: PSS (CLEVIOS P AR 4083) from H. C. Starck Is spun onfrom solution.

Thereafter, the organic materials specified below are applied by vapordeposition to the cleaned substrate at about 10⁻⁷-10⁻⁹ mbar at a rate ofapprox. 0.5-5 nm/min. The hole conductor and exciton blocker applied tothe substrate is Ir(DPBIC)₃ with a thickness of 45 nm, of which thefirst 35 nm are doped with MoO_(x) to improve the conductivity,

(for preparation see Ir complex (7) in the application PCT/EP/04/09269).

Subsequently, a mixture of emitter and of the compound Ma1 is applied byvapor deposition with a thickness of 40 nm, the latter compoundfunctioning as a matrix material. Subsequently, the material Ma1 isapplied by vapor deposition with a thickness of 10 nm as an exciton andhole blocker.

Next, an electron transporter BCP(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) is applied by vapordeposition in a thickness of 20 nm, as are a 0.75 nm-thick lithiumfluoride layer and finally a 100 nm-thick Al electrode. All componentsare adhesive-bonded to a glass lid in an inert nitrogen atmosphere.

To characterize the OLED, electroluminescence spectra are recorded atdifferent currents and voltages. In addition, the current-voltagecharacteristic is measured in combination with the light output emitted.The light output can be converted to photometric parameters bycalibration with a photometer. The lifetime t_(1/2) of the diode isdefined by the time taken for the luminance to fall to 50% of itsinitial value. The lifetime measurement is carried out at a constantcurrent.

For the different emitters in the above-described OLED structure, thefollowing electrooptical data are obtained:

Cd/A t_(1/2) @ 1000 nits (normalized Emitter CIE @ 300 nits to the valueof CEm2) Em1-i 0.22/0.37 23.2 cd/A 594% Em3-i 0.18/0.28 19.5 cd/A 135%Em2-i 0.17/0.25 24.5 cd/A 245% CEm2 0.20/0.35 10.3 cd/A 100%

Example 18

Comparison of Different Isomers of One Emitter

By way of example, the influence of the different isomers on the OLEDperformance is shown in two cases. For the different emitters andisomers in the above-described OLED structure, the followingelectrooptical data are obtained:

Cd/A t_(1/2) @ 1000 nits (normalized Emitter CIE @ 300 nits to the valueof Em1-s) Em1-s 0.19/0.31 18.2 cd/A 100% Em1-i 0.22/0.37 23.2 cd/A 406%Cd/A t_(1/2) @ 1000 nits (normalized Emitter CIE @ 300 nits to the valueof Em2-s) Em2-s 0.21/0.35 15.4 cd/A 100% Em2-i 0.17/0.25 24.5 cd/A 178%

Example 19

Influence of a Mixed Electron Conductor Layer

The example which follows shows the influence of the doping of the BCPelectron conductor layer with Liq.

The following OLED structure is used:

ITO—40 nm AJ20—1000—35 nm Ir(DPBIC)₃ mixed with MoO_(x)—10 nmIr(DPBIC)₃—40 nm Ma1 mixed with 20 wt % Em1-i—5 nm Ma1—40 nm electronconductor—1 nm Liq-100 nm Al. The preparation of the OLED is carried outin analogy to Example 17.

Electron Cd/A t_(1/2) @ 1000 nits (normalized conductor CIE @ 300nits tothe value of BCP) BCP 0.22/0.36 16.8 cd/A 100% BCP:Liq 50% 0.21/0.3621.7 cd/A 170%

Example 20

Complex Em9-s:

Imidazoliumiodide C6 corresponds to a pre-intermediate of the compound“example 1” in WO 2006056418. The synthesis is carried out in analogy tothe synthesis of the compound “example 1” in WO 2006056418.

2.0 g (6.4 mmol) of imidazoliumiodide C6 and 0.75 g (3.2 mmol) Ag₂O arestirred in 170 ml anhydrous acetonitrile for 4 h at 50° C. The solventis then removed in vacuo.

To the residue 170 ml anhydrous toluene is added and 3.6 g (2.1 mmol)chlorodimer D1 are added. Subsequently it is heated under reflux for 24h. After cooling the reaction mixture is filtered. The filtrate is freedfrom solvent in vacuo. To the residue methylene chloride is added,washed with water, reduced after drying and purified by chromatography(cyclohexane/acetic ester), where by 0.26 g Em9-s are isolated (6%) and0.63 g of a mixed fraction of complex Em9-s with not complexedphenylimidazol-ligand as well as 0.10 mg of a further complex withinverse ligand stoichiometry. Further 1.3 g of chlorodimer D1 (36%) arereisolated.

¹H-NMR (CD₂Cl₂, 400 MHz):

δ=0.83 (d, 3H), 0.89-0.96 (m, probably interpreted as 4×d, 12H), 1.00(d, 3H), 1.13 (d, 3H), 1.15 (d, 3H), 1.98 (sept, 1H), 2.31 (sept, 1H),2.70 (sept, 1H), 2.74 (sept, 1H), 3.21 (s, 3H), 6.10 (dd, 2H), 6.37-6.45(m, 4H), 6.56-6.65 (m, 4H), 6.70 (dd, 1H), 6.83 (me, 1H), 6.95 (d, 1H),7.06 (me, 1H), 7.19 (me, 2H), 7.25-7.31 (m, 4H), 7.44-7.50 (m, 3H).

MS (Maldi):

m/e=979 (M+H)⁺

photoluminescence (in film, 2% in PMMA):

λ_(max)=456, 487 nm, CIE: (0.20; 0.30)

Example 21

Complex Em9-i:

A solution of 0.17 g of complex Em9-s in 2000 ml acetonitril areirradiated at 15° C. for 9.5 h with a blacklight-blue-lamp (Osram,L18W/73, λ_(max)=370-380 nm). The solvent is removed in vacuo. Theresidue is purified by chromatography (cyclohexane/acetic ester). 0.055g of Em9-i (32%, contaminated with traces of a further complex) areobtained as well as 0.075 g of reisolated Em9-s (44%) are reisolated.

¹H-NMR [CD₂Cl₂, 400 MHz, sample comprises traces of a further complexobservable for example at 0.77 (m), 0.83 (d), 1.04 (d), 1.21 (m), 1.92(sept), 2.34 (sept), 7.20-7.23 (m), 7.31-7.34 (m)]:

δ=0.65 (d, 3H), 0.77 (d, 3H), 0.85 (d, 3H), 0.97 (d, 3H), 0.98 (d, 3H),1.02 (d, 3H), 1.13 (d, 6H), 1.82 (sept, 1H), 2.33 (sept, 1H), 2.54(sept, 1H), 2.67 (sept, 1H), 3.04 (s, 3H), 6.09 (dd, 2H), 6.37 (td, 1H),6.40-6.44 (m, 3H), 6.50 (m, 1H), 6.59 (d, 1H), 6.61 (td, 1H), 6.68 (d,1H), 6.70 (d, 1H), 6.72 (d, 1H), 6.86 (d, 1H), 6.96 (br.s, 1H), 7.14(me, 2H), 7.20-7.23 (m, 1H), 7.23-7.31 (m, 3H), 7.44-7.50 (m, 3H).

MS (Maldi):

m/e=979 (M+H)⁺

photoluminescence (in film, 2% in PMMA):

λ_(max)=457, 485 nm, CIE: (0.17; 0.26)

The photoluminescence quantum efficiency of the isomer Em9-i has the1.14-fold value of the quantum efficiency of the isomer Em9-s.

Example 22 Complex Em10-s1.3-Diphenyl-4,5-di-o-tolyl-imidazolium-tetrafluoroborate C7

Step 1: Preparation of 2-anilino-1,2-di-o-toluene-ethanone

A solution of 18.00 g (74.91 mmol) o-toluoine are dissolved in 100 mlanhydrous toluene and 21.00 g (224.9 mmol) of anilin and 0.2 g conc. HClare added at room temperature. The reaction mixture is heated for 10hours to boiling under reflux, where by the water formed is revolvedout. After cooling to room temperature the reaction mixture is dilutedwith 100 ml acetic ester and then shaked two times with 70 ml 1 n HCleach. Subsequently the organic phase is washed with 100 ml of water and70 ml of brine, dryed over magnesium sulfate and reduced to a yellowresin. The crude product is purified chromatographically on silica gelwith methylene chloride as eluent. After removal of the solvent 19.6 g(83%) of a yellow oil are obtained.

Step 2: Preparation of N-(2-oxo-1,2-di-o-tolyl-ethyl)-N-phenyl-formamide

A solution of 19.50 g (58.7 mmol) 2-anilino-1,2-di-o-tolyl-ethanone in80 ml of tetrahydrofuran is meaned with 7.80 g (88.1 mmol)acetformylanhydride and stirred for 17 hours at room temperature. Thereaction mixture is reduced at a rotarap to a syrup and purified atsilica gel with a petrol ether-acetic ester solution as eluent at firstin a ratio of 10:1 then 1:1. After removal of the solvent 18.4 g (91%)of a nearly colorless syrup are obtained.

Step 3: Preparation of3-phenyl-4,5-di-o-tolyl-oxazolium-tetrafluoroborate

To 9.80 g (55.9 mmol) of 50% tetrafluoroboric acid 63 g trifluoroaceticanhydride are added by a syringe at 5-10° C. in 15 min (exothermicl).The cooled solution is subsequently added dropwise to a suspension of20.00 g (55.3 mmol)N-(2-oxo-1,2-di-o-tolyl-ethyl)-N-phenyl-formamide in60 g of trifluoroacetic anhydride at room temperature in 10 min, wherebythe temperature rises to 28° C. The reaction mixture is stirred for 3hours at 20-25° C. and then reduced at a rotarap to an oil. Afteraddition of 100 ml diethylether 9.7 g (55.3 mmol) 50% tetrafluoroboricacid are added dropwise by stirring, whereby a precipitate is formed.After stirring for one hour the precipitate is drawn off, washed threetimes with 10 ml diethyl ether each and dried. 22.55 g (99%) of acolorless powder are obtained.

Step 4: Preparation of1,3-diphenyl-4,5-di-o-tolyl-imidazolium-tetrafluoroborate C7

To a suspension of 3.50 g (8.47 mmol)3-phenyl-4,5-di-o-tolyl-oxazolium-tetrafluoroborate in 35 ml of ethanol1.58 g (16.9 mmol) of aniline are added. After stirring for 45 min atroom temperature, the solution is reduced to an orange colored resin andsubsequently 15 mol sulfuric acid are added. The solution is stirred for2 hours at room temperature. The reaction solution is stirred in 300 mlice water where by a precipitate is formed. The suspension is stirredfor a further hour and then filtered over a suction filter. The residueis washed with water and sucked to dryness to a large extend. Theresidue is stirred in an Erlenmeyer flask with 40 ml of diethyl ether,sucked and washed with 10 ml of diethyl ether. The stirring in diethylether with subsequent suction is repeated two times. After drying 3.10 g(71% d.th.) of a colorless powder are obtained.

Complex Em10-s:

A suspension of 1.61 g (3.30 mmol)1,3-diphenyl-4,5-di-o-tolyl-imidazolium-tetrafluoroborate in 25 ml oftoluene are stirred for 15 min under argon at room temperature and thencooled to 0° C. 12.6 ml (6.29 mmol) 0.5 Mpotassium-bis(trimethylsilyl)-amide in toluene are added with 1 min. Thereaction solution is then stirred for 15 min at 0-12° C., andsubsequently, 2.50 g (1.50 mmol) bis(iridium-p-chloro-complex) D1 areadded. It is purged with 5 ml of toluene. The orange-yellow suspensionis heated under reflux to boiling. After 75 min the reaction solution iscooled to room temperature diluted with 20 ml acetic ester and thenextracted two times with 20 ml of phosphate buffer solution (ph 7). Theorganic phase is separated, dryed over sodium sulfate and then reducedto dryness. The solid is shortly heated in 150 ml of methanol underreflux to boiling. After cooling of the suspension to 50° C. the solidis sucked, washed two times with 10 ml of methanol each and dryed. 2.52g of a yellow solid are obtained. The filtrate is reduced to 40 ml andstirred overnight at room temperature. The precipitate is sucked, washedwith a small amount of methanol and dried. 0.28 g of a yellow solid areobtained, which is combined with the residue.

Therefore, alltogether 2.80 g (78% of th.) of a yellow solid melting at282-283° C. are obtained.

MS (Maldi):

m/e=1197.4 (M+H)⁺

Photoluminescence (in film, 2% in PMMA):

λ_(max)=464, 493 nm, CIE: (0.19; 0.35)

Example 23

Complexes Em10-i and Em10-i*:

0.50 g (0.42 mmol) of Em10-s are dissolved in 300 ml of acetonitril andirradiated with a mercury pressure dipping lamp TQ 150 (365 nm, 150 W)for 5.5 hours. The solution is freed from the solvent. The residue isdissolved in 30 ml of methanol by heating. After cooling the precipitateis sucked, washed with methanol and dried. The complex isomer Em10-i[0.19 g (38%)] is obtained as yellow powder melting at 316-317° C.

MS (Maldi):

m/e=1196.7 (M)⁺

Photoluminescence (in film, 2% in PMMA):

λ_(max)=460, 491 nm, CIE: (0.18; 0.32)

The filtrate is reduced to dryness, stirred with 10 ml of n-pentane,sucked, washed with pentane and dried. The complex isomer Em10-i* [0.16g (32%)] is obtained as ocher yellow solid melting at 207-209° C.

MS (Maldi):

m/e=1197.8 (M+H)⁺

Photoluminescence (in film, 2% in PMMA):

λ_(max)=458, 490 nm, CIE: (0.19; 0.33)

I) Diode Examples Concerning Em1-s Example 24—Influence of the MatrixMaterials on Em1-s

Diode Structure:

ITO—PEDT:PSS—35 nm Ir(DPBIC)₃ mixed with 10 wt.-% MoO_(x)—10 nmIr(DPBIC)₃—40 nm Matrix MaX mixed with 15 wt.-% Em1-s-10 nm LB1—20 nmelectron conductor BCP—0.70 nm LIF—100 nm Al.

The preparation of the diode is carried out in analogy to Example 17.

Exciton and hole blocker LB1:

EQE @ 300 nits and Matrix Voltage in Cd/A @ normalized to the value“MaX” CIE V @ 300 nits 300 nits of Ma2 Ma2¹ 0.20/0.36 8.8 10.1 100% Ma30.20/0.32 5.5 20.5 166% Ma4² 0.19/0.32 6.5 16.3 134% Ma5 0.20/0.31 6.213.9 115% Ma6³ 0.19/0.30 6.2 22.8 195% ¹In this case 40 nm BCP were usedas electron conductor. ²In this case 30 nm BCP were used as electronconductor. ³In this case AJ20-1000 of Plexcore instead of PEDT:PSS wereused as hole injection layer.

Structures of the matrices “MaX” (=Ma2−Ma6) and description of theirsynthesys in WO2010/079051:

Synthesis of MaX described in Matrix ″MaX″ WO2010/079051 as StructureMa2 BS 10

Ma3 BS15

Ma4 BS18

Ma5 BS20

Ma6 BS 31

II) Diode Examples Concerning Em1-i Example 25—Influence of the MatrixMaterials on Em1-i

Structure A: ITO—AJ20—1000—35 nm Ir(DPBIC)₃ mixed with 50 wt.-% MoO₃—10nm Ir(DPBIC)₃—40 nm “MaX” mixed with 20 wt.-% Em1-i—5 nm “MaX”—40 nmelectron conductor BCP: Liq 50 wt.-%—1 nm Liq-100 nm Al. The preparationof the diode is carried out in analogy to Example 17.

Structure B: ITO—AJ20—1000—35 nm Ir(DPBIC)₃ mixed with 10 wt.-% MoO₃—10nm Ir(DPBIC)₃—40 nm “MaX” mixed with 15 wt.-% Em1-i—10 nm LB1—20 nmelectron conductor BCP—0.70 nm LiF—100 nm Al. The preparation of thediode is carried out in analogy to Example 17.

EQE @ 300 nits Matrix Diode Voltage in Cd/A@ normalized MaX structureCIE V @ 300 nits 300 nits to the value of Ma7 Structure A 0.22/0.36 5.818.8 100% Ma8 Structure B 0.23/0.38 7.0 17.3  91% Ma9 Structure A¹0.23/0.38 4.3 17.9  95% ¹In this case 5 nm Ma1 are used as excition andhole blocker.

Structures of the Matrices MaX and Description of their Synthesis inWO2010/079051:

Matrix Compound in MaX WO2010/079051 Structure Ma7 BS26

Ma8 BS29

Ma9 BS28

Example 26—Influence of the Matrix Materials on Em1-i

ITO—AJ20—1000-10 nm Mal mixed with 10 wt.-% MoO_(x)—10 nm Ma10 mixedwith 15 wt.-% Em1-i and 15 wt.-% Ma1—5 nm Ma1—20 nm electron conductorBCP mixed with 20 wt.-% Ma1—1 nm Cs₂CO₃— 100 nm Al. The preparation ofthe diode is carried out in analogy to Example 17.

The synthesis of matrix material Ma10 is described in JP2009046408,compound B, [0039], p. 13.

Ma10

Matrix Voltage MaX CIE in V @ 300 units Ma10 0.19/0.35 3.8

The invention claimed is:
 1. A heteroleptic complex of the generalformula (I)

wherein: M is a metal atom selected from the group consisting of Ir andPt, A¹, A² are each independently N or C, n, m are each independently 1or 2, where, if M is Pt, the sum of n and m is 2, or, if M is Ir, thesum of n and m is 3, R¹ is a linear or branched alkyl radical optionallyinterrupted by at least one heteroatom, optionally bearing at least onefunctional group and having 1 to 20 carbon atoms, cycloalkyl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 3 to 20 carbon atoms, substitutedor unsubstituted aryl radical optionally interrupted by at least oneheteroatom, optionally bearing at least one functional group and having6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 5 to 18 carbon atoms and/orheteroatoms, R², R³ are each independently hydrogen, linear or branchedalkyl radical optionally interrupted by at least one heteroatom,optionally bearing at least one functional group and having 1 to 20carbon atoms, cycloalkyl radical optionally interrupted by at least oneheteroatom, optionally bearing at least one functional group and having3 to 20 carbon atoms, substituted or unsubstituted aryl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 6 to 30 carbon atoms, substitutedor unsubstituted heteroaryl radical optionally interrupted by at leastone heteroatom, optionally bearing at least one functional group andhaving 5 to 18 carbon atoms and/or heteroatoms, R⁴, R⁵, R⁶, R⁷ are eachindependently hydrogen, substituent with donor or acceptor action,linear or branched alkyl radical optionally interrupted by at least oneheteroatom, optionally bearing at least one functional group and having1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by atleast one heteroatom, optionally bearing at least one functional groupand having 3 to 20 carbon atoms, substituted or unsubstituted arylradical optionally interrupted by at least one heteroatom, optionallybearing at least one functional group and having 6 to 30 carbon atoms,substituted or unsubstituted heteroaryl radical optionally interruptedby at least one heteroatom, optionally bearing at least one functionalgroup and having 5 to 18 carbon atoms and/or heteroatoms, or R⁴ and R⁵or R⁵ and R⁶ and/or R⁶ and R⁷ together form a saturated, unsaturated oraromatic carbon ring optionally interrupted by at least one heteroatomand having a total of 5 to 30 carbon atoms or heteroatoms, R⁸, R⁹ areeach independently a free electron pair if A¹ or A² is N, or, if A¹ orA² is C, hydrogen, linear or branched alkyl radical optionallyinterrupted by at least one heteroatom, optionally bearing at least onefunctional group and having 1 to 20 carbon atoms, cycloalkyl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 3 to 20 carbon atoms, substitutedor unsubstituted aryl radical optionally interrupted by at least oneheteroatom, optionally bearing at least one functional group and having6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 5 to 18 carbon atoms and/orheteroatoms, R¹⁰ is a linear or branched alkyl radical optionallyinterrupted by at least one heteroatom, optionally bearing at least onefunctional group and having 1 to 20 carbon atoms, cycloalkyl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 3 to 20 carbon atoms, substitutedor unsubstituted aryl radical optionally interrupted by at least oneheteroatom, optionally bearing at least one functional group and having6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radicaloptionally interrupted by at least one heteroatom, optionally bearing atleast one functional group and having 5 to 18 carbon atoms and/orheteroatoms, R¹¹, R¹², R¹³, R¹⁴ are each independently hydrogen,substituent with donor or acceptor action, linear or branched alkylradical optionally interrupted by at least one heteroatom, optionallybearing at least one functional group and having 1 to 20 carbon atoms,cycloalkyl radical optionally interrupted by at least one heteroatom,optionally bearing at least one functional group and having 3 to 20carbon atoms, substituted or unsubstituted aryl radical optionallyinterrupted by at least one heteroatom, optionally bearing at least onefunctional group and having 6 to 30 carbon atoms, substituted orunsubstituted heteroaryl radical optionally interrupted by at least oneheteroatom, optionally bearing at least one functional group and having5 to 18 carbon atoms and/or heteroatoms, or R¹¹ and R¹² or R¹² and R¹³and/or R¹⁴ together form a saturated, unsaturated or aromatic carbonring optionally interrupted by at least one heteroatom and having atotal of 5 to 30 carbon atoms and/or heteroatoms, R¹ and R¹⁴ optionallytogether form a saturated or unsaturated, linear or branched bridgeoptionally comprising heteroatoms, aromatic units, heteroaromatic unitsand/or functional groups and having a total of 1 to 30 carbon atomsand/or heteroatoms, to which a substituted or unsubstituted, five-toeight-membered ring comprising carbon atoms and/or heteroatoms isoptionally fused, if A¹ is C, R⁷ and R⁸ optionally together form asaturated or unsaturated, linear or branched bridge optionallycomprising heteroatoms, aromatic units, heteroaromatic units and/orfunctional groups and having a total of 1 to 30 carbon atoms and/orheteroatoms, to which a substituted or unsubstituted, five- toeight-membered ring comprising carbon atoms and/or heteroatoms isoptionally fused.
 2. The heteroleptic complex according to claim 1,wherein: M is Ir, A¹, A² is C, n, m are each independently 1 or 2, wherethe sum of n and m is 3, R¹ is a linear or branched alkyl radical having1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6to 30 carbon atoms, substituted or unsubstituted heteroaryl radicalhaving 5 to 18 carbon atoms and/or heteroatoms, R², R³ are eachindependently hydrogen, linear or branched alkyl radical having 1 to 20carbon atoms, substituted or unsubstituted aryl radical having 6 to 30carbon atoms, substituted or unsubstituted heteroaryl radical having 5to 18 carbon atoms and/or heteroatoms, R⁴, R⁵, R⁶, R⁷ are each hydrogenor R⁴ and R⁵ or R⁵ and R⁶ or R⁶ and R⁷ together form a saturated,unsaturated or aromatic ring optionally interrupted by at least oneheteroatom and having a total of 5 to 30 carbon atoms and/orheteroatoms, R⁸, R⁹ are each hydrogen, R¹⁰ is a linear or branched alkylradical having 1 to 20 carbon atoms, substituted or unsubstituted arylradical having 6 to 30 carbon atoms, and R¹¹, R¹², R¹³, R¹⁴ are eachindependently hydrogen or linear or branched alkyl radical having 1 to20 carbon atoms, R¹ and R¹⁴ optionally together form a saturated orunsaturated, linear or branched bridge optionally comprisingheteroatoms, aromatic units, heteroaromatic units and/or functionalgroups and having a total of 1 to 30 carbon atoms and/or heteroatoms, towhich a substituted or unsubstituted, five- to eight-membered ringcomprising carbon atoms and/or heteroatoms is optionally fused, R⁷ andR⁸ optionally together form a saturated or unsaturated, linear orbranched bridge optionally comprising heteroatoms, aromatic units,heteroaromatic units and/or functional groups and having a total of 1 to30 carbon atoms and/or heteroatoms, to which a substituted orunsubstituted, five- to eight-membered ring comprising carbon atomsand/or heteroatoms is optionally fused.
 3. The heteroleptic complexaccording to claim 1, wherein: M is Ir, A¹, A² are each N or C, whereA¹=N when A²=C and A¹=C when A²=N n, m are each independently 1 or 2,where the sum of n and m is 3, R¹ is a linear or branched alkyl radicalhaving 1 to 20 carbon atoms, substituted or unsubstituted aryl radicalhaving 6 to 30 carbon atoms, substituted or unsubstituted heteroarylradical having 5 to 18 carbon atoms and/or heteroatoms, R², R³ are eachindependently hydrogen, linear or branched alkyl radical having 1 to 20carbon atoms, substituted or unsubstituted aryl radical having 6 to 30carbon atoms, substituted or unsubstituted heteroaryl radical having 5to 18 carbon atoms and/or heteroatoms, R⁴, R⁵, R⁶, R⁷ are each hydrogen,or R⁴ and R⁵ are R⁵ and R⁶ or R⁶ and R⁷ together form a saturated,unsaturated or aromatic ring optionally interrupted by at least oneheteroatom and having a total of 5 to 30 carbon atoms and/orheteroatoms, R⁸, R⁹ are each independently a free electron pair if A¹ orA² is N, or, if A¹ or A² is C, hydrogen, linear or branched alkylradical having 1 to 20 carbon atoms, substituted or unsubstituted arylradical having 6 to 30 carbon atoms, substituted or unsubstitutedheteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms, R¹⁰is a linear or branched alkyl radical having 1 to 20 carbon atoms,substituted or unsubstituted aryl radical having 6 to 30 carbon atoms,and R¹¹, R¹², R¹³, R¹⁴ are each independently hydrogen or linear orbranched alkyl radical having 1-20 carbon atoms, R¹ and R¹⁴ optionallytogether form a saturated or unsaturated, linear or branched bridgeoptionally comprising heteroatoms, aromatic units, heteroaromatic unitsand/or functional groups and having a total of 1 to 30 carbon atomsand/or heteroatoms, to which a substituted or unsubstituted, five- toeight-membered ring comprising carbon atoms and/or heteroatoms isoptionally fused, if A¹ is C, R⁷ and R⁸ optionally together form asaturated or unsaturated, linear or branched bridge optionallycomprising heteroatoms, aromatic units, heteroaromatic units and/orfunctional groups and having a total of 1 to 30 carbon atoms and/orheteroatoms, to which a substituted or unsubstituted, five- toeight-membered ring comprising carbon atoms and/or heteroatoms isoptionally fused.
 4. The heteroleptic complex according to claim 1,wherein: M is Ir, A¹ is C, A² is N or C, n, m are each independently 1or 2, where the sum of n and m is 3, R¹ is a linear or branched alkylradical having 1 to 20 carbon atoms, substituted or unsubstituted arylradical having 6 to 30 carbon atoms, substituted or unsubstitutedheteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms, R²,R³ are each independently hydrogen, linear or branched alkyl radicalhaving 1 to 20 carbon atoms, substituted or unsubstituted aryl radicalhaving 6 to 30 carbon atoms, substituted or unsubstituted heteroarylradical having 5 to 18 carbon atoms and/or heteroatoms, R⁴, R⁵, R⁶ areeach independently hydrogen, linear or branched alkyl radical having 1to 20 carbon atoms, substituted or unsubstituted aryl radical having 6to 30 carbon atoms, R⁷, R⁸ together form an unsaturated C₂ bridge, towhich a substituted or unsubstituted, five- to eight-membered ringcomprising carbon atoms and/or heteroatoms, may be fused, R⁹ is a freeelectron pair if A² is N or, if A² is C, hydrogen, linear or branchedalkyl radical having 1 to 20 carbon atoms, substituted or unsubstitutedaryl radical having 6 to 30 carbon atoms, substituted or unsubstitutedheteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms, R¹⁰is a linear or branched alkyl radical having 1 to 20 carbon atoms,substituted or unsubstituted aryl radical having 6 to 30 carbon atoms,and R¹¹, R¹², R¹³, R¹⁴ are each independently hydrogen or linear orbranched alkyl radical having 1 to 20 carbon atoms, R¹ and R¹⁴optionally together form a saturated or unsaturated, linear or branchedbridge optionally comprising heteroatoms, aromatic units, heteroaromaticunits and/or functional groups and having a total of 1 to 30 carbonatoms and/or heteroatoms, to which a substituted or unsubstituted, five-to eight-membered ring comprising carbon atoms and/or heteroatoms isoptionally fused.
 5. The heteroleptic complex according to claim 1,wherein R¹ is an aryl radical which has 6 to 30 carbon atoms and issubstituted in the ortho,ortho′ positions in each case by a linear orbranched alkyl radical having 1 to 10 carbon atoms.
 6. The heterolepticcomplex according to claim 1, wherein R¹ and R¹⁴ together form asaturated or unsaturated, linear or branched bridge optionallycomprising heteroatoms, aromatic units, heteroaromatic units and/orfunctional groups and having a total of 1 to 30 carbon atoms and/orheteroatoms, to which a substituted or unsubstituted, five- toeight-membered ring comprising carbon atoms and/or heteroatoms isoptionally fused.
 7. The heteroleptic complex according to claim 1,wherein R⁴ and R⁵, R⁵ and R⁶ or R⁶ and R⁷ together form a cycle of thegeneral formula (IIa) or (IIb)


8. The heteroleptic complex according to claim 1, which has one of thefollowing configurations Ma, IIIb, IVa or IVb:


9. A process for preparing a heteroleptic complex according to claim 1by contacting at least one precursor compound comprising the metal M andthe at least one ligand which, in the complexes of the general formula(I), is attached to M via noncarbene bonds with at least one ligandwhich, in the complexes of the general formula (I), is attached to M viaat least one carbene bond, or the ligand precursor thereof, for examplea corresponding imidazolium salt, or by contacting at least oneprecursor compound comprising the metal M and a ligand which, in thecomplexes of the general formula (I), is bonded to M via at least onecarbene bond with at least one ligand which, in the complexes of thegeneral formula (I), is attached to M via noncarbene bonds.
 10. An OLEDcomprising at least one heteroleptic complex according to claim
 1. 11.An OLED comprising a heteroleptic complex according to claim 1 and atleast one compound of the formula (X)

in which T is NR⁵⁷, S, O or PR⁵⁷; R⁵⁷ is aryl, heteroaryl, alkyl,cycloalkyl or heterocycloalkyl; Q′ is —NR⁵⁸R⁵⁹, —P(O)R⁶⁰R⁶¹, PR⁶²R⁶³,S(O)₂R⁶⁴, —S(O)R⁶⁵, —SR⁶⁶, —OR⁶⁷, or

wherein R⁶⁸, R⁶⁹ are each independently alkyl, cycloalkyl,heterocycloalkyl, aryl or heteroaryl; y, z are each independently 0, 1,2, 3 or 4; R⁵⁵, R⁵⁶ are each independently alkyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl, SiR⁷⁰R⁷¹R⁷², a group Q′ or a groupwith donor or acceptor action; a″ 0, 1, 2, 3 or 4; b′ 0, 1, 2 or 3; R⁵⁸,R⁵⁹ together with the nitrogen atom form a cyclic radical which has 3 to10 ring atoms and may be unsubstituted or substituted by one or moresubstitutents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl,heteroaryl and a group with donor or acceptor action and/or may be fusedto one or more further cyclic radicals having 3 to 10 ring atoms, wherethe fused radicals may be unsubstituted or substituted by one or moresubstituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl,heteroaryl and a group with donor or acceptor action; R⁷⁰, R⁷¹, R⁷²,R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷ are each independently aryl,heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, or two units of thegeneral formula (X) are bridged by a linear or branched, saturated orunsaturated bridge, optionally interrupted by at least one heteroatom,by a bonding or by O.
 12. The OLED according to claim 11 comprising atleast one compound of formula (XI) or (XI*)

wherein T is NR⁵⁷, S, O or PR⁵⁷; R⁵⁷ is aryl, heteroaryl, alkyl,cycloalkyl or heterocycloalkyl; Q′ is —NR⁵⁸R⁵⁹, —P(O)R⁶⁰R⁶¹, PR⁶²R⁶³,S(O)₂R⁶⁴, —S(O)R⁶⁵, —SR⁶⁶ or —OR⁶⁷; R⁷⁰, R⁷¹, R⁷² are each independentlyaryl, heteroaryl, alkyl, cycloalkyl, heterocycloalkyl, wherein of atleast one of the radicals R⁷⁰, R⁷¹, R⁷² comprises at least two carbonatoms or OR⁷³, R⁵⁵, R⁵⁶ are each independently alkyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl, a group Q or a group with donor oracceptor action; a′, b′ are for the compound of formula (XI): eachindependently 0, 1, 2, 3; for the compound of formula (XI*) a′ is 0, 1,2 and b is′ 0, 1, 2, 3, 4; R⁵⁸, R⁵⁹ together with the nitrogen atom forma cyclic radical which has 2 to 10 ring atoms and may be unsubstitutedor substituted by one or more substituents selected from alkyl,cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor oracceptor action and/or may be fused to one or more further cyclicradicals having 3 to 10 ring atoms, where the fused radicals may beunsubstituted or substituted by one or more substituents selected fromalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group withdonor or acceptor action; R⁷³ is independently SiR⁷⁴R⁷⁵R⁷⁶, aryl,heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, optionallysubstituted with a group OR⁷⁷ R⁷⁷ is independently SiR⁷⁴R⁷⁵R⁷⁶, aryl,heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, R⁶⁰, R⁶¹, R⁶², R⁶³,R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, R⁷⁴, R⁷⁵, R⁷⁶ are each independently aryl,heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, or two units of thegeneral formulae (XI) and/or (XI*) are bridged by a linear or branched,saturated or unsaturated bridge, optionally interrupted by at least oneheteroatom or by O, wherein said bridge is bonded in the generalformulae (XI) and/or (XI*) each time instead of R⁷¹ to the Si-atoms. 13.The OLED according to claim 12, wherein in the compounds of the generalformulae (XI) or (XI*) R⁷⁰ and/or R⁷¹ and/or R⁷² are aromatic units ofthe general formulae (XIi) and/or (Xii*)


14. A light-emitting layer comprising at least one heteroleptic complexaccording to claim
 1. 15. An OLED comprising a light-emitting layeraccording to claim
 14. 16. The OLED according to claim 10, whichcomprises an electron-transporting layer comprising at least twodifferent materials, of which at least one material iselectron-conductive.
 17. The OLED according to claim 16, wherein theelectron-transporting layer comprises at least one phenanthrolinederivative and optionally comprises at least one alkali metalhydroxyquinolate complex.
 18. A device selected from the groupconsisting of illuminating elements, stationary visual display units andmobile visual display units, comprising at least one OLED according toclaim
 10. 19. An OLED comprising a heteroleptic complex according toclaim
 1. 20. The OLED according to claim 19, wherein the heterolepticcomplex is an emitter, matrix material, charge transport material orcharge blocker.